Environment in Submarine

ENVIRONMENT IN SUBMARINES
MVR Koteswara Rao
DEFENCE RESEARCH & DEVELOPMENT ORGANISATION

MINISTRY OF DEFENCE
NEW DELHI 110 011
2001
DRDO Monographs/Special Publications Series

MVR Koteswara Rao
Series Editors
Editor-in-Chief
Editors
Dr Mohinder Singh
Ashok Kumar, A Saravanan
Asst. Editor
Editorial Asst.
Ramesh Chander
RK Saxena
Production
Printing
Marketing
JV Ramakrishna, SK Tyagi
RK Dua
2001, Defence Scientific Information & Documentation Centre

(DESIDOC), Defence R&D Organisation, Delhi-110 054.
All rights reserved. Except as permitted under the Indian Copyright
Act 1957, no part of this publication may be reproduced, distributed
or transmitted, stored in a database or a retrieval system, in any
form or by any means, electronic, mechanical, photocopying,
recording, or otherwise, without the prior written permission of
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The views expressed in the book are those of the author only. The
editors or publisher do not assume responsibility for the
statements/opinions expressed by the author.
ISBN: 81-86514-08-2
Printed and published by Director, DESIDOC, Metcalfe House, Delhi-110 054.
CONTENTS
Preface
xi
Acknowledgements
xiii
CHAPTER 1
SUBMARINE DEVELOPMENT
1.1
How Does a Submarine Function?
1.2
Logistics
1.3
The Crew
CHAPTER 2
LAYOUT OF SUBMARINES & OPERATIONS
2.1
Men & Metabolic Activity
12
2.2
Typical Calculation of Carbon Dioxide

Generated in Submarine
2.3
Metabolic Organic Compounds
15
2.4
Engines & Batteries
18
2.5
Scrubbers
19
2.6
Air-conditioning
20
2.7
Firefighting
20
2.8
Escape Operation
22
2.9
Emergency Surfacing
23
2.10
Panelling, Flooring & Degreasing
23
2.11
Food Cooking/Warming
25
2.12
Cigarette Smoking
27
15
(vi)
CHAPTER 3
POLLUTANTS IN SUBMARINE COMPARTMENTS
29
3.1
Carbon Monoxide
30
3.2
Carbon Dioxide
31
3.3
Hydrogen
32
3.4
Stibine
32
3.5
Sulphuric Acid Aerosol
32
3.6
Oxides of Sulphur & Nitrogen
33
3.7
Organics
33
3.7.1
Polynuclear Aromatic Hydrocarbons
33
3.7.2
Hydrocarbons
35
3.8
Hydrazine
35
3.9
Monoethanolamine
35
3.10
Chlorine
36
3.11
Microbes
36
CHAPTER 4
EXPOSURE TO INDOOR POLLUTANTS & HEALTH
EFFECTS
37
4.1
Carbon Monoxide
38
4.2
Carbon Dioxide
39
4.3
Oxides of Sulphur & Nitrogen
39
4.4
40
4.5
Stibine
40
4.6
Chlorine
40
4.7
Hydrazine
40
4.8
Organics
41
4.9
Synergistic Effects
41
4.10
Effect of Indoor Air Pollution in Submarine
42
4.10.1
Remedies
42
4.11
Risk Assessment
44
4.11.1
Role of Risk Assessment in Submarine

Environment
45
(vii)
CHAPTER 5
DAMAGE TO MATERIALS & EQUIPMENT
47
CHAPTER 6
AIR QUALITY STANDARDS IN SUBMARINES
49
6.1
Development of OSHA, ACGIH & Submarine

Standards
49
6.2
Additional Standards
50
CHAPTER 7
AIR POLLUTION MODELLING IN SUBMARINES
53
7.1
Mass-Balance Equation
53
7.2
Case Study
54
CHAPTER 8
MONITORING AIR QUALITY IN SUBMARINES
57
8.1
Sampling Techniques
57
8.2
Analytical Methods
58
8.2.1
Carbon Monoxide
58
8.2.1.1
Non-Dispersive Infrared Absorption
58
8.2.1.2
Comowarn
60
8.2.1.3
Detector Tube
60
8.2.1.4
Iodine Pentoxide Method
61
8.2.2
Carbon Dioxide
62
8.2.2.1
Titrimetric Method
62
8.2.2.2
Electrochemical Measurement
63
8.2.2.3
Refractive Index Method
63
8.2.2.4
Chemical Detector Tube Method
64
8.2.3
Hydrogen
64
8.2.3.1
Thermal Conductivity Analyser
64
8.2.3.2
Mass Spectrometric Method
65
8.2.4
Oxygen
65
(viii)
8.2.4.1
Volumetric Method
65
8.2.4.2
Paramagnetic Oxygen Analyser
65
8.2.4.3
Electrochemical Analyser
67
8.2.5
Hydrocarbons
67
8.2.5.1
Chemical Detector Tube
67
8.2.5.2
Methanometer
67
8.2.5.3
NDIR
67
8.2.5.4
Gas Chromatographic Techniques
68
8.2.5.5
GC-MS Technique
68
8.2.5.6
Photoacoustic Spectrometry
68
8.2.6
68
8.2.6.1
Collection of Polynuclear Aromatic

Hydrocarbons from Air
69
8.2.6.2
Detection of Polynuclear Aromatic Hydrocarbons
69
8.2.7
Freons
70
8.2.7.1
GC-MS Technique
70
8.2.7.2
Freon Meter
70
8.2.7.3
Detector Tube
71
8.2.7.4
IR and PAS Techniques
71
8.2.8
Organics
71
8.2.8.1
Acrolein
71
8.2.8.2
Formaldehyde
72
8.2.8.3
Monoethanolamine
73
8.2.9
Chlorine
73
8.2.9.1
Colorimetric Method
73
8.2.9.2
Detector Tube
74
8.2.10
Halocarbons
75
8.2.11
Nitrogen Dioxide
75
8.2.11.1
Saltzman Method
75
8.2.11.2
Detector Tube
76
8.2.11.3
Chemilluminescence Method
76
8.2.12
Hydrogen Chloride
76
(ix)
8.2.12.1
Fajans Method
76
8.2.12.2
Volhard Method
77
8.2.13
Hydrazine
77
8.2.13.1
Oxidation with Iodine
77
8.2.13.2
Oxidation with KMnO4
77
8.2.13.3
Detector Tube
77
8.2.14
Ammonia
78
8.2.14.1
Titration Method
78
8.2.14.2
Nesslers Method
78
8.2.14.3
Detector Tube Method
78
8.2.14.4
Ion Selective Electrode Method
79
8.2.15
Stibine
79
8.2.15.1
Rhodamine Method
79
8.2.15.2
Methyl Fluorone Method
80
8.2.15.3
Detector Tube Method
81
8.2.16
81
8.2.17
Conclusion
82
CHAPTER 9
SOME CONCEPTS OF AIR POLLUTION CONTROL
IN SUBMARINES
85
9.1
Metabolic Process
85
9.2
Control Operations
86
CHAPTER 10
AIR REVITALISATION IN SUBMARINES
89
10.1
Oxygen Supply
91
10.1.1
High Pressure Gas Storage
92
10.1.2
Liquefied Oxygen
92
10.1.3
Chlorate Candles
92
10.1.4
Potassium Superoxide
93
10.1.5
Oxygen Supply from Water Electrolysis
93
(x)
10.1.6
Solid Polymer Electrolysis
94
10.2
Hydrogen Eliminators
96
10.3
Carbon Monoxide Conversion
96
10.3.1
Hopcalite
97
10.3.2
Metal-impregnated Active Carbon
97
10.3.3
Activated Carbon
98
10.4
Carbon Dioxide Control
100
10.4.1
Adsorption on Molecular Sieves
100
10.4.1.1
Preparation
101
10.4.1.2
Identification
101
10.4.1.3
Adsorption Characteristics
101
10.4.1.4
Tailored MS
102
10.4.1.5
Temperature Swing Molecular Adsorption Process

102
10.4.1.6
Pressure Swing Molecular Adsorption Process
102
10.4.2
Sodalime
103
10.4.3
Lithium Hydroxide
104
10.4.4
105
10.4.5
Carbon Dioxide Removal using Wet MEA

Scrubber
105
10.4.6
Solid Amine Scrubber
107
10.5
Freon Control
108
10.6
Aerosol Removal
108
Appendix A
111
Appendix B
113
Appendix C
115
Appendix D
117
Appendix E
119
Appendix F
121
Index
123
PREFACE
The technical monograph Environment in Submarines is first
of the kind in the field of environmental science relating to closed
spaces. The need of such a document covering all facets of the
enclosed environment has been felt since long. Not enough literature
exists on this subject, mainly because an enclosed environment
cannot be perceived in day-to-day events, and also not many
investigators have access to this. Environment in the submarine
is thus a fully air-tight one, wherein no external air finds its way
inside and the internal air requiring constant revitalisation. In
this monograph, effort has been made to picturise the actual
conditions prevailing in the submarine and also to describe a variety
of problems faced by the habitants. The monograph depicts the
successful trials to solve these problems to ensure a safer
environment. A vivid description was given about the R&D work in
monitoring, control and management of the environment. The
author himself was engaged in these activities over the last two
decades and has drafted realistic information in this monograph.
The monograph has been divided into ten chapters and
contains six appendices apart from subject index.
Place: Hyderabad
Date: September 2001
MVR Koteswara Rao
ACKNOWLEDGEMENTS
The author expresses his gratitude to the authorities of the
Defence Research & Development Organisation, Ministry of Defence,
Government of India, for providing facilities, training and
encouragement to bring out this technical monograph. He is
particularly thankful to the Director, Naval Material Research
Laboratory, Ambernath and the Director, Naval Research &
Development, New Delhi for permission to publish this work. The
author also expresses his sincere gratitude to the colleagues of the
Biology, Environmental Studies Division and to Shri Shrikumar
(Steno-typist) for constant help.
CHAPTER 1
SUBMARINE DEVELOPMENT
The submarine is a sea-going vessel designed to navigate

underwater in dived condition as well as on sea surface. Efforts to
design and develop this class of seafaring vessels date back to early
1776. The earliest submarine, Turtle was designed by David Bushnell
in 1776 at Yale University, USA. Later, Nautilus, another new design
submarine was built by Robert Fulton in the US. The next discovery
was the submarine Hunley, which really operated underwater and
sank the Union ship Houstanic by ramming the surface ship with a
charge of gun powder in 1864. The submarine Holland was built for
the US Navy by John P. Holland in 1900. The next design, an
unproven submarine model by name Skipjack, came into existence
in 1911 with a diesel engine. Subsequently, based on designs made
in the US and Germany, a series of submarines and U-boats were
produced, which were employed in World Wars I and II respectively.
The chronological development of submarines and their unique
underwater performance starting from 1776 to 1963 is shown in
Table 1.11.
Table 1.1. Chronological development of submarines and their
unique performance
Year
Submarine
Unique performance
Designer
1776
Turtle
First war submarine
1800-1
Nautilus
Forerunner of
today's submarine
Robert Fulton
1864
Hunley
Sank the warship

Houstanic
James R. McClinton
& Baxter Watson
David Bushnell
Contd ....
Environment in Submarines
Year
Submarine
Unique performance
1897
Arganaut
Odd-shaped
Simon Lake
1900
Holland
First accepted
ubmarine
John P. Holland
1911
Skipjack
First use of diesel engine
1914-17 U-Boats
(Germany)
World War I naval

submarines
1914
Skipjack
First American submarine

to cross the Atlantic
1936
Fleet
submarine
Launched by USA
1944
U-Boats
(Germany)
Snorkel attachment for

greater underwater diving
1945
Japanese
I fleet
Sunk warship
US Indianapolis
1954
Nautilus
First nuclear powered

submarine
1958
Nautilus
Crosses the North Pole

underwater
1959
Triton
Worlds largest submarine
1959
George
Washington
First Polaris carrying

submarine commissioned
1961
E. Allen
Nuclear warship
S.Houstan, etc.
1963
Lafayette
class
Nuclear warship
1967
Toti
Italian, single hull type
1967
Sjoormen
Swedish, single hull type
1969
Class 206
German, single hull type
1975
Agosta
French, double hull type
Source: Gilmore, H.H., 1962.
Designer
Due to the efforts of

Admiral Hymen &
G. Rickover
Submarine Development
1.1
HOW DOES A SUBMARINE FUNCTION?
The submarine is a shell enclosing a volume that weighs

less than an equal volume of water and hence it floats over water.
When it is required to dive underwater, its weight is increased by
intake of sufficient seawater into the ballast tanks built in around
the hull until its weight is greater than the weight of water it
displaces. When it is desired to bring the submarine to surface, the
water from the ballast tanks is expelled out by compressed air. The
depth for navigation is adjusted using control surfaces referred
to as forward/aft planes.
The submarine body is shaped in a pointed manner to
provide streamlining to minimise hydrodynamic resistance. A sketch
of a submarine is shown in Fig.1.1. The forward motion of the vessel
through water is achieved by means of a propeller and the steering
to right or left by a rudder. When the vessel is fully submerged, two
sets of hydroplanes press against the resisting water and make
the submarine go up or down. They also control the angle at which
the vessel has to operate. The superstructure of a submarine has a
snorkel which allows the submarine to operate submerged (at
periscope depth) while taking in air from the atmosphere through
the snorkel tube for running its diesel engines. There are no decks
on the submarine superstructure. All machinery, weaponry and
utilities are enclosed in the interior of the capsule.
In actual operation, diesel-electric power is used for
propulsion of submarine on surface and electric power (from storage
batteries) for underwater propulsion, the reason being that lot of
air is required for burning diesel oil when the ship is underwater;
so much of air otherwise is not available at that time when the
whole submarine is sealed from the outside environment. After the
introduction of snorkel by the Germans during World War II, the
normal underwater depth range with diesel power has been extended
up to the periscope height level. With the advent of atomic power
for nuclear submarines, the scarcity of power is no more there and
travel underwater with the same prevailing air has become possible
for extended periods, even upto six months. The nuclear fission
occurring in an atomic reactor fitted on board a submarine gives
enormous power supply to drive generators and produce electricity
sufficient for continuously running the vessel for years together.
STERN
RUDDER
PROPELLER
HULL
Figure 1.1. Sketch of a submarine
STABILISER WITH HYDROPLANES (AFT)
SUPERSTRUCTURE
FIN
HYDROPLANES (FORWARD)
PERISCOPE
BOW
4
Table 1.2. Typical nuclear submarines and their characteristics
Type
Year of commission
(approx)
No. of men on board
Nautilus
1954
90
Seawolf
1957
90
Skate
1957
85
Triton
1959
135
Skipjack
1959
80
George Washington
1959
100
Halibut
1960
100
Tulli bee
1960
50
Thresher
1961
85
E. Allen
1961
100
Lafayette
1963
100
Valiant
1963
75
Source: Norman Polmer, (1963).
In Table 1.2, the chronological development and

commissioning of nuclear submarines and their capabilities is shown.
All these nuclear ships range in tonnage within 3000-6000, length
250-450 ft, breadth approximately 65 ft, and possess one or two
propellers. They have enormous internal space, accommodate more
crew members than what a conventional submarine holds, and also
carry large quantity of weaponry 2. Also, life supporting oxygen
required for crew is generated on board and the released carbon
dioxide is eliminated in situ by compression. Remarkably, both
conventional and atomic submarines are required for the rescue
purposes by all countries, as the conventional small submarines
cruise around coasts and the atomic powered vessels guard the
oceans in the geographical region3.
1.2
LOGISTICS
Conventional submarines carry men and weaponry

required for wars around the coastline and operate in shallow waters.
The normal mission period ranges from a few days to a month.
During this period, on each day the submarine has to come up to
snorting (at periscope level) for atleast 4 hr when the ships ventilation
practice, battery charging, waste removal and similar functions are
taken up. The underwater diving period in these submarines range
from 20 to 100 hr for typical exercises. Atomic submarines perform
unending surveillance in oceans and also near ice poles. Many
facilities in these vessels are in-built and automatic in nature.
Radar, which is a normal detection system cannot be used
in submarines as the electromagnetic radiation cannot penetrate
much in seawater. Transmission of visual light is also not possible
at the depth of about 200 m and hence the periscope vision is also
not possible. Seawater medium allows the passage of sound energy
only and hence submarines depend on the sound signal
transmissions through sonar for detection of other ships and
submarines. For this purpose, during construction, sonar domes
that are transparent to sound are erected over the hull to facilitate
detection of ships or submarines. The signals of sound are processed
by sonar equipment after eliminating the contributions from selfnoise of ship and ambient noise.
The operation snorting at snorkel permits the submarine
crew to perform many functions. Whether in conventional or nuclear
submarine, one can spot the enemy installations by operating at
the snorkel level using the periscope. Signal transmission at shallow
water level can be achieved with more ease. Diesel engines can be
started to recharge the batteries as well as ventilate the interior
cabins and compartments4.
Additional information on several aspects has to be
collected by a submariner while cruising, viz., (i) the hydrology
parameters, (ii) temperature of seawater, (iii) salinity, (iv) density,
(v)tide and current, (vi) seasonal characteristics of seawater,
(vii)magnetic features, (viii) knowledge of underwater explosions,
(ix)gaseous emissions in sea, (x) mountain ranges penetrating into
the seas, (xi) behaviour of sea animals and their hindrance to sound
transmission, and (xii) radiation over the outer atmosphere in seas.
The indoor air quality in submarine compartments also has to be
monitored periodically to ensure clean air for breathing purposes5.
1.3
THE CREW
Conventional submarines of tonnages 500-1500 generally

accommodate 10-40 crew members on board the vessel. In nuclear
submarines, upto 150 members can be very easily accommodated.
Power supply and space are two limiting factors in any submarine.
As the number of crew members in a submarine increases, the
demand for more quantity of oxygen from environment exists and
eventually more release of carbon dioxide into the enclosed space.
The absorption of oxygen and the release of carbon dioxide
phenomena are governed by respiration and a reasonable respiratory
quotient RQ, which is a ratio of carbon dioxide produced to oxygen
consumed, namely, 0.85 for submarines, explains the good state of
environment in submarine. The crew have to perform several hard
tasks on board. A psychological condition of restricted movement
in closed chambers sets in. They have to eat mostly canned foodstuff
throughout the cruises. Cigarette smoking is also prohibited inside
the vessel. Even when the ship is snorting, the clearance of smoke
is not that fast. On the whole, the crew are subjected to restricted
movement inside and this is not akin to the movement in a ship.
The risk of enemy spotting the submarine and endangering it is
also high and hence high alertness has to be displayed by crew
members at all times.
REFERENCES
1.
2.
3.
4.
5.
Gilmore, H.H. Model submarines for beginners. Harper

&Row Publishers, New York, 1962. pp. 12-13.
Norman, Polmer. Atomic submarines. D Van Nostrand Co.
Inc., New Jersey, 1963. pp. 268-70.
Captain Moore, John, E. Janes Fighting Ships. 1977-78 (Ed.)
Janes Yearbooks, London, 1977. pp. 1-4.
Admiral Shekhawat, V.S. Submarines: Their capabilities
and deployment. Indian Defence Review, 1990, 7, 51-59.
Shrivastava, A.K. & Koteswara Rao, M.V.R. Environment in
submarine compartments. Defence Sci. J., 1987, 37(2),
257-67.
CHAPTER 2
LAYOUT OF SUBMARINES & OPERATIONS
To understand the environment and its influence on men

working in submarine compartments (which are totally sealed units
while underwater), the knowledge of its layout and operations
carried out on board by men and machinery is essential. A general
layout of interior space of a submarine is shown in Fig.2.1. In
this, the entire portion available for movement in the ship is divided
into four functional work centres; namely, the engine room, the
combat information centre, the living spaces and the battery pits.
Out of these, the former three portions are sub-divided into several
units depending on the logistic functions.
In a naval submarine, the shell is made of steel. The
internal cover is the pressure hull and is constructed in such a
manner that it withstands the external hydrostatic pressure. Over
this another hull is built up through connections with ribs; and
this gives a streamlined shape to the submarine, providing an even
walking platform for the crew while entering/leaving harbour. In
between the outer hull and the inner hull are laid the ballast tanks,
which provide air cushion around the pressure hull while afloat.
These tanks may hold diesel fuel also; if required. For diving, ballast
tanks (except those containing fuel) are flooded with seawater by
gravity (always). Compressed air is used to blow (empty) the ballast
tanks so that the submarine comes on surface.
A typical layout of a modern submarine is shown in Fig.2.1.
The pressure hull is cylindrical in the midst of the vessel and is
Note:
This outer hull or casing is free-flooding and therefore the underlying pressure hull
also comes in direct contact with seawater).
Source: Ingenier konter Lubeck Prof Gabler Nach Gmbh, Lubeck.
Figure 2.1. Interior space of a submarine
1. Engine room, 2.Engine control room, 3. Operations centre, 4. Communications room, 5. Sick bay, 6. Commanding officer's cabin, 7.
Galley, 8. Officers' living quarters, 9. NCOs' living quarters, 10. Enlisted men's living quarters, 11. Aft diving room, 12. Forward diving
room, 13.Steering unit, 14. Torpedo tubes, 15. Fuel tank, 16. Battery tanks, 17. Periscope well.
10
Layout of Submarines & Operations
shaped into conical sections at both aft and forward ends. There
may be other tanks holding other provisions like fresh water,
lubricating oil, etc. There are other components of vital systems,
like HP air bottles, anchor and chain cables and various flaps which
are in between the pressure hull and outer hull. By means of
compressed air supplied from HP air bottles through the emergency
blowing system, seawater can be blown from ballast tanks and the
submarine surfaces.
As seen in Fig. 2.1, the aft side machinery compartment
contains engines for propulsion, propeller shaft, steering gear for
the steering rudder, stern plane, aft trim tank, diesel generator
sets and various auxiliary machinery. Also located down below the
diesel generators are the main fuel tanks and lubricating oil tanks.
The space in front of the engine room bulkhead contains
the aft battery room (first partial storage of batteries) in the lower
part and adjoining this are the fresh water tanks on either side.
Above the battery room is situated the control room positioning
the switch boards and remote controls for the machinery. The main
ballast and bilge pumps, compressors and controllers are also
housed in the starboard space of this floor.
The next space towards forward section is the combat
information centre (CIC). The upper section of CIC houses the
steering gear controls and instruments for operating the steering
rudder, hydroplanes, detection devices, navigation and fire control
equipment. The periscope, whip antenna and snorkel penetrate
outside through the pressure hull section at this position of CIC.
Two compensating tanks and two midship ballast tanks which vent
seawater into the sea through valves are also located in the bottom
of CIC.
The second partial battery room is situated in the lower
forward position of CIC and adjoined by two freshwater tanks. Above
the second partial battery room lie the captains cabin and officers
accommodation and a sanitary room with toilet.
In front of the forward battery room is the space allotted
for holding six torpedo tubes. A further storage space for storing
eight torpedoes also exists. The area aft of the torpedo tubes serves
11
12
as crew quarters and sanitary blocks. The bow plane motors are
situated under the torpedo storage space.
Finally, the outer hull envelopes the conical sections of
the pressure hull forward and aft. The keel is constructed over the
pressure hull. The free-flooding narrow superstructure above the
pressure hull connects the forward and aft sections of the outer
hull. The keel structure is very rigid so that the submarine can
dock on it safely.
2.1
MEN & METABOLIC ACTIVITY
For the given layout of a submarine (Fig. 2.1), the free

space in the interior is about 900 m 3 (excluding engine room,
which is about 150 m 3). This space can accommodate all the
functionaries including about 40 men. In a hypothetical case, the
CIC volume is taken as 300 m3, the aft 300 m3 and both the battery
pits about 300m3. The distribution of men would be three for engine
room, eight for CIC, and about fifteen performing jobs at aft
compartment and elsewhere. Approximately, one-third of the crew
will be resting in shifts in living spaces.
Maintenance of clean air and comfort is the primary task
of the environmental management programme in a submarine. The
1
composition of clean air is recorded in Table 2.1 . This quality of
air has to be maintained in submarine even after many air
exchanges or revitalisation. Comfort in an environment is a pleasant
factor based on physical, physiological and psychological
parameters and it enhances the productivity in work. It has been
stated in literature2 that a comfortable physical condition exists
when the surrounding temperature is 24.5C, relative humidity 40
per cent and air velocity 0.25m/s. Clothing also plays an important
role in giving comfort, and therefore submarine crew are provided
with a balanced clothing that will dissipate the heat from the body.
The chief life support for men in a submarine is clean air. Oxygen
is the constituent which is required for providing energy. The human
body temperature is correctly maintained at 36.7 0.3C
continuously owing to the burning of carbohydrates and fats by
oxygen. Oxygen present in air (~ 21 per cent) gets absorbed in
human body to the extent of 4per cent and about 16 per cent
returns in the exhaled air.

Table 2.1. Chemical composition of dry atmospheric air
Component
Nitrogen
Oxygen
Argon
Volume
(per cent)
78.05
20.91
0.93
Carbon dioxide
0.03
Methane
1.00 ppm
Neon
18 ppm
Krypton
0.5 ppm
Xenon
0.1 ppm
Hydrogen
0.4 ppm
Ozone
70 ppb
Water vapour
Traces
Source: Work, K. and Warner, C.F. 1976.
The daily requirement of air for a person in a submarine

works out in the range of 1500-4000 litres, of which one-fifth is
energy generating oxygen. This figure is worked on the basis of
average number of breaths a person takes per hour under the
submarine working conditions.
Even though large quantity of oxygen (21 per cent) of air
is available for the human being, only a limited quantity (~4 percent)
is exchanged in the lungs with carbon dioxide. This phenomenon
is due to the adaptation of human lungs to a limited quantity of
oxygen. The partial pressure of carbon dioxide in a human lung is
about 40Torr (corresponding to 5.6 per cent of carbon dioxide in
air). The exhaled air however contains 4 per cent of carbon dioxide.
The efficiency of exchange of oxygen to carbon dioxide expressed
as respiratory quotient (RQ)
RQ = VO2 (in)/V CO2 (out)
which is 0.82 for human beings. This ratio exists for a good exchange
between oxygen and carbon dioxide in a clean environment. However,
in a submarine which is a sealed unit, when carbon dioxide level
goes upto 1.0-1.5 per cent in air, this ratio gets disturbed and
symptoms of hypoxia appear amongst crew members. The tolerance
of carbon dioxide by human beings is given in Fig. 2.2.
13
4
CONCENTRATION-VOL (per cent)
14
. . . . . . . SAFE LIMIT
0.5
0.03
0
10
15
25
20
30
35
40
EXPOSURE PERIOD (Days)
Figure 2.2. Carbon dioxide tolerance

Source: Beat Meyer, 1983.
The oxygen consumption rates for various types of work

including submarine operations is shown in Table 2.2.
Table 2.2. Oxygen consumption by men for various activities
Activity
Sleeping
Consumption
(l/man/hr)
15
Sitting
18
Standing
25
Submarine condition
(near value)
27
Source: Harper, N.G. and Davis, D.N. (1974).
The exhaled air of men contains water to the extent of

47Torr (or 6 per cent volume of air). The exchange of water takes
place between human body and outside through the skin and lungs
and this is dependent on the type of work. This water content adds
upto the moisture already prevalent in the ambient air. It may be
stated in this connection that the partial pressure of water in air
which balances the RH to 40 per cent in air is a matter of comfort.
2.2
TYPICAL CALCULATION OF CARBON DIOXIDE

GENERATED IN SUBMARINE
The following example presents an idea of the carbon

dioxide generation during underwater cruise in a submarine:
Internal volume of submarine
600 m3
Total crew
30
Operating period
24 hr
Start point
Level of CO2 at start point (ambient air)
0.035 %
Level of CO2 in submarine at snorkel at any

later stage with ventilation
Maximum level allowed for CO2
0.1 %
1.0 %
Rate of CO2 production
25 l/man/hr
30 men (of crew) produce CO2
30 25 = 750 l/hr
Now, to calculate the time to reach the partial level of CO2

from 0.1-1.0 per cent in a free volume of 600 m3, the difference of
increase in concentration of carbon dioxide from initial snorkel stage
to exhalted level is 1.0-0.1 = 0.9 per cent. Total volume of carbon
dioxide generated from men in the submarine is
600 0.9/100 = 5.4m3 = 5400 l
Since the rate of production from 30 men per hour
corresponds to 750 litres, this 5400 litres quantity must have been
generated in 7.2 hr as
provided that no absorption processes are started in the submarine

during this period.
2.3
METABOLIC ORGANIC COMPOUNDS
Metabolic substances of the categoriesalcohols,

ketones, keto-acids, amino acids, urea, aldehydes, particulates,
etc. are emanated from men and find their way into the closed
spaces of submarines. The effects which these compounds produce
are allergy, itching and undesirable odour. In addition, several
microbes are also generated through a number of steps in the
metabolism. A list of organics (organic compounds) that exist in
cabin air is given in Table 2.3.
15
16
Table 2.3. Organic compounds found in submarine cabins
Compound
name
Formula
Highest
chemical
concentration
found
Acetylene
HCCH
0.5 ppm
50 ppm
Acetic acid
H3CCOOH
Traces
10 ppm
Acrolein
H2C=CH-CHO
Traces
Ammonia
NH3
Benzene
C6H6
71 ppm
1,3 -
C2H5 CH3
Traces
1 ppm
MAC*
0.5 ppm
Ill effects
Strong acid
odour
Disagreeable
odour,choking
50 ppm
Strong odour,
irritating to
nose and eyes
25
Aromatic smell
Aromatic smell
Dimethyl
5-ethyl
CH 3
benzene
Ethylene
H2C=CH2
Traces
50
(MIRAN spec)
p-Ethyl
toluene
CH3
Traces
200 ppm
Ethyl
mercapton
C2H5SH
Freon-114
Aromatic smell
C2H5
Traces
10 ppm
CF2Cl
CF2Cl
71 ppm.
1000 ppm
Freon-12
CCl2F2
70 ppm
1000 ppm
Formaldehyde
HCHO
0.4 ppm
Gasoline
(Hydrocarbons
other than CH)
Hydrazine
N2H4
Methane
CH4
Methanol
CH3OH
25 ppm
118 ppm
(MIRAN spec)
6 ppm
3 ppm
Garlic smell
Strong odour
500 ppm
Characteristic
smell
1 ppm
Strong
ammoniacal
smell
50
Characteristic
marshy smell
Narcotic odour
irritant
Contd .......

Compound
name
Formula
Highest
chemical
concentration
found
MAC*
Methanolamine
H2COHNH2
<1 ppm
Mesitylene
(CH3 ) 3C6H3
Traces
Propane
CH3CH2CH3
Traces
1000 ppm
Xylenes
(O, m & P.)
(CH3 ) 2C6H4
Traces
100 ppm
3 ppm
Ill effects
Ammonia
smell
Aromatic
smell
* Max. allowable concentration
The human wastes must be carefully managed in the

confined spaces of submarine3. These constitute mainly exhaled
air, saliva, skin scales, urine and faeces. Exhaled air contains, in
addition to carbon dioxide, slight ammonia, acetone and traces of
carbon monoxide. The sneeze aerosols contain many inorganic salts,
enzymes and organics. Sweat contains calcium and other metallic
ions, chloride, and amino acids, e.g., arginine, histidine and
threonine in small quantities. Ammonia and urea are also present
in traces. Lactic acid is present to the extent of 5 mg/ml. Fatty
acids such as butyric, valeric and caproic acids amount to about
1.2 per cent by weight of sweat. Some vitamins of B-complex group
and glycerides are also present in traces. The organic constituents
of sweat depend mostly on the diet intake and health condition of
a man.
The human skin scales that contaminate the submarine
environment emanate from dried skin, hair loops, scalp and sebum.
The total scales reported per man is 3 g everyday of which the
forehead contributes approximately 20 mg. Sebum contains many
fine scales from which four or five bacteria also generate. A total of
about 160 mg of bacteria or micro-organisms are released per man
from a nuclear submarine4. It was reported that the particulate
load of indoor component of nuclear submarine in 100 hr cruise is
about 0.4 mg/m3.
Saliva and tears, which are resultant of body actions
amount to about 1 g/day/man and these contain mainly
ammonia and amino acids. Human urine is composed of urea,
creatinine, uric acid, hippuric acids and some harmones.
The volatiles of urine and also some decomposed products
result in foul odours. Faeces produce carbon dioxide, ammonia,
17
18
methane and some obnoxious organic compounds. The odour

threshold of some organic compounds which enter the indoor
spaces of submarines is recorded in Table 2.4.
Table 2.4. Odour thresholds for some organic compounds
Chemical
Odour threshold
Acetic acid
1.0
Acetone
100
Monomethyl amine
Trimethyl amine
Ammonia
Sour
Chemical smell
0.021
Fishy
0.0021
Fishy
46.8
Carbon disulphide
Vegetable sulphide
Odour description
(ppm)
0.21
Chlorine
0.314
Bleach
Diphenyl sulphide
0.0047
Burnt, rubbery
Formaldehyde
1.0
Hay & showlike
Ethyl hydroxide (EtOH)
100
Methylene chloride
214
Phenol
Sweet
0.047
Medicinal
Pyridine
0.021
Pungent
Nitrobenzene
0.0047
Aniline
1.0
Diethyl formamide
2.4
100.0
Ammoniacal
Pungent
ENGINES & BATTERIES
Many conventional submarines operate on propulsion

systems based on lead-acid storage batteries, electric drive motors,
and diesel engines which use snorkel for air inlet. The diesel engines
are of 1000-1500 rpm capacity. When the submarine is on the
surface, diesel-electric propulsion is adopted while the batteries
are charged. When the boat is on the snorkel (a condition with
diving readiness at periscope depth), the diesel engines operate
through the generators, the submarine is driven on electric motors,
and the batteries charged. Lastly, when the submarine is diving
underwater, the batteries provide entire power supply through the
electric drive motors.
In Fig. 2.1, the battery room is shown at two different
locations. On each side about 260 batteries are stacked. The voltage
conditions are approximately the same for all lead-acid cells
(2.5 to 2.7 V) whereas the capacity in ampere hours and the electric
energy in kilowatt hours depend on the size and number of cells
connected. Individual cells are combined into partial batteries to
afford higher voltage and current (approx. 200 amperes) by
connecting their terminals with bus bars depending on the voltage
requirement. The partial batteries may be connected in series or
parallel. The highest voltage available on the ship when these
batteries are connected in series accumulates to 1,000 V. Generally
two or four cells are combined in one box made up of FRP, and
these larger units are wedged in place in the battery room on wooden
wedges and laid in stable manner. The battery rooms are closed by
covers.
The diesel fuel employed in the engines has a low sulphur
content, usually below 0.5 per cent. The lead-acid batteries are
manufactured using lead plates (which have 7-10 per cent of
antimony in it) and dipped in concentrated sulphuric acid having
sp.gr.1.3 5,6.
When the submarine is on surface or snorting at the
periscope depth, the diesel engines work. During this process,
exhaust gases, namely, carbon monoxide, carbon dioxide, sulphur
dioxide, nitrogen oxides and organic compounds are generated.
These gases leave the submarine through the exhaust provided in
the engine compartment. The air from the ambient atmosphere at
sea surface is utilised for burning the fuel. Slight contamination of
air, if any, in the engine compartment with these pollutants is
periodically checked and recorded. When the submarine goes
underwater, the ventilation into the engine room from outside is
cut off and no diesel oil is permitted to be consumed in the engines.
The batteries energise the electric motors and provide the electric
supply for the ship. During discharge of the batteries, gases such
as hydrogen, stibine and sulphuric acid aerosol are generated in
reasonable quantities. The general ventilation system takes care of
CIC, aft and battery and torpedo places of the submarine. The
gases emanating from the battery are monitored at several points
near source and occupational places.
2.5
SCRUBBERS
An monoethanolamine (MEA)scrubber is widely employed

in some classes of submarines for the removal of carbon dioxide in
indoor air 7. The air requiring purification is passed via the
filter into the absorber section of the plant where it is forced
through a porous plate, on the top of which MEA is continuously
19
20
sprinkled to form a foamed bed. The intimate contact between

impure air and MEA allows the carbon dioxide to be completely
absorbed instantaneously. The pure air is later led to the washing
filters and hence into the atmosphere. The carbon dioxide rich MEA
is lifted to the regeneration unit where it is allowed to trickle through
a column containing hot steam, decomposes into MEA and carbon
dioxide respectively at the end of the column. The carbon dioxide
is compressed in a volume and discharged overboard and MEA
condensed, collected and recycled. Several MEA scrubber designs
are available nowadays in the market. During the processes of
absorption-desorption of carbon dioxide in the MEA scrubber, a
small quantity of MEA in the form of vapours enter the submarine
environment. It therefore becomes mandatory to monitor MEA in
submarine compartments, which have been fitted with these
scrubbers. The physicochemical characteristics of MEA are recorded
in Table 2.5.
Table 2.5. Physicochemical properties of MEA
2.6
Chemical formula
HOCH2CH2NH2
Colourless
Liquid, B.P. 172C

Sp. gr. 1.02 at 20C
Odour
Mildly ammoniacal
1 ppm
2.54 mg/m3
TLV
3 ppm
AIR-CONDITIONING
The CIC and the captains cabin of a submarine are

maintained at a temperature of 20C. The CIC houses all electronic
equipment and microprocessors, which give commands to various
systems. The capacity of air-conditioning in a submarine varies
according to the size of cabins. Freons of the type CFC-114 are
employed in air-conditioning plants8 and occasionally leakage of
the gas into the cabins does take place.
2.7
FIREFIGHTING
Firefighting equipment in the form of cylinders are

provided on board the submarine. These cylinders are filled up
with most common freon 1211. The cylinders are to be placed in
positions away from heat generating points, as otherwise any freon
coming out of them is likely to decompose at hot surface into
hydrogen chloride and lower hydrocarbons. Freons and

halocarbons are effective firefighting agents. They envelope the
fire instantaneously and deprive the oxygen supply as a result of
which the fire is extinguished. Moreover, no residue from the fire
extinguisher is left behind. There is only one drawback in the use
of CFCs in the fire extinguishers its ozone-depleting power in
the stratosphere of the earth. The ozone-depleting power of typical
freon substances is shown in Table 2.6. Some typical properties
of refrigerants from air-conditioning are recorded in Table 2.7 9.
Currently, efforts are being put to replace the freons
(including freon 1211) with low ozone-depleting chemicals. The
phasing out of freons is governed under the Montreal Protocol,
under which all developed countries would phase out the CFC's
by 2000 and developing countries by 2005.
Table 2.6. (a) Ozone depleting CFCs
Group CFC No.
A
Ozone depletion
index
Usage
R 11
1.0
Blowing agent for foam insulators
R 12
1.0
Refrigerant, wide use
R 113
0.8
Cleaner and solvent
R114
1.0
Refrigerant for chilled water

plants navy(submarine) usage
R 115
0.6
Not used alone, but in mixtures
Halon1211
3.0
Extensive firefighting, in
portable extinguishers
1301
10.0
2402
6.0
Firefighting, room flooding etc.

Not much use
(b) Less common refrigerant mixtures

Nomenclature
CFC No.
Proportion
Ozone depleting index
R 500
R 12/ R 152 A
73.8/26.2
0.74
R 501
R 22/ R 12
75/25
0.25
R 502
R 22/ R 115
48.8/51.2
0.30
Source: Tillin, A.J. CFCs, The Royal Navy and the ozone layer. J. Nav Eng. 1990, 32(2),
232-33.
21
22
Table 2.7. Properties of refrigerants (chlorofluorocarbons)
CFC
No.
Formula
B.P.
(C)
11
CCl3F
74.7
()
()
5 to 60
12
CCl2F2
21
()
()
90 to 60
All low temperature

commercial coolers
brine coolers, etc.
are most widely used
13
CClF3 144.5
()
()
125 to 20
Ultralow application
and refrigeration
22
CHClF2 41.4
()
()
100 to 60
Home air-conditioners,
farm freezers.
113
C Cl2F
C ClF2
117.6
()
()
Up to 0
114
CClF2
CClF2
38.4
()
()
70 to 60
Combination
CFCs
28
Toxicity Flamability
+/
+/
( C)
()
Normal
usage
temperature
()
Variable
Use
Air-conditioners
Air-conditioners,
water chillers
Drinking water
coolers, industrial
water chillers
Industrial
applications
Source: Tillin A.J. J. Naval Engg., 1990.
2.8
ESCAPE OPERATION
All classes of submarines provide a passage for the escape

of personnel to the surface through conning tower in case of sinking.
During this operation, normal ventilation practices adapted in the
submarine would not be reaching the places through which the men
have to escape. Hence, a provision is made for the supply of oxygen in
that environment from a rapid device which generates this gas. It is
an oxygen candle, which is builtup from potassium chlorate and oxides
of barium, etc. On burning this candle in the escape areas, free oxygen
will come out, which will balance the level of oxygen in the enclosed
space. Alongwith oxygen, a little of chlorine is also generated
simultaneously. However, the barium oxide present in the candle
immediately reacts with free chlorine and eliminates this gas10. It is,
however, mandatory to monitor the level of chlorine in the environment
,
and see that its level is below the toxic limit (1.0ppm). Chlorine present
in these spaces is eliminated by passing the air through soda lime
canisters (already functioning for absorbing carbon dioxide that is
generated in these areas).
2.9
EMERGENCY SURFACING
When a submarine is in danger while operating in deep

waters (approx. 300 m), it has to be rapidly brought to the surface.
The hydroplanes are operated to bring the submarine to the surface.
Also the ballast tanks can be emptied by blowing large quantities
of compresed air. The latest technique is to employ hydrazine-based
generator modules in the forward ballast tanks and trigger all these
at the same instance to blow the main ballast thereby achieving
the operation in about 10-13 s. In the gas generator, hydrazine
comes in contact with an oxidant (nitric acid) and instantaneously
produces large quantities of nitrogen
gas, which renders
this operation. The indoor air of
submarine, under these
conditions, contains hydrazine vapour to a significant extent11.
The spontaneous release of nitrogen from hydrazine
on reaction with oxidant has been schematically shown by the
equation:
The physicochemical properties of hydrazine are recorded

in Table 2.8.
Table 2.8.
Physicochemical properties of hydrazine
Chemical formula
H 2N-NH 2
Properties
Colourless liquid,
BP 113 C Sp. gr. 1.01mg/cc
Vapour pressure at 20 C 16 mm.
Pungent and ammoniacal odour,
Carcinogenic chemical reaction. Any
Oxidising agent reacts spontaneously
producing nitrogen.
1 ppm = 1.33 mg/m 3
Source: Encyclopaedia of Chem. Tech., 1975.
2.10
PANELLING, FLOORING & DEGREASING
Particle board and plywood are two important materials

used in the interior decor of submarines. The panels usually are
made of phenol-formaldehyde or urea-formaldehyde-based resins
clad on particle board, or by pressing wood chips in a hot press.
The resin content is usually 7-10 per cent by weight, and freshly
fabricated panels have a pronounced formaldehyde smell, on
account of the incompletely reacted formaldehyde, which dissipates
into the open environment. Variable quantities of formaldehyde
23
24
emanate in indoor spaces where insulation was done using ureaformaldehyde resin depending upon the occupancy conditions,
weather (humidity, temperature) and seasons, etc. and a steady
air flow that takes in the vapours of formaldehyde. The vapours
are strongly absorbed on moist wood, walls and when dry conditions
prevail, they once again liberate out. Interior grade of plywood
bonded with urea formaldehyde has an emission rate of 34 mg/m 2
per day and particle board has a rate of 25 mg/m2 per day. Both
are reasonable emittors of formaldehyde. The release of
formaldehyde at various locations of house indoors is recorded in
Table 2.9.
The formaldehyde released into the atmosphere in
mobile homes empanelled with resins is of the order of
0.35 0.4 ppm and this figure is hundred times more than that
prevalent in rural homes. The observed level of formaldehyde in
wall cabinets fitted to walls in homes reach 24 ppm, but this
slowly comes down when ventilation prevails. It is expected that
in a closed space, e.g., wardroom of a submarine, similar levels
of formaldehyde may prevail in the 25 m2 total area panelled with
these boards. The Environmental Protection Agency (USA) has
recorded correlations between formaldehyde and clinical effects
in men2,12.
Floor covering mats and carpets are often glued to the
surface of floor by means of adhesives. These chemicals are
absorbed on the rags of the carpet to some extent and then liberate
slowly into the environment. Furthermore, floor covering carpets
absorb the fumes or gases from the interior spaces and slowly
release the same into the space13-15.
Table 2.9. Release of formaldehyde at various locations
Location
Concentration (ppb)
Basement
60-170
Bedroom
Outdoors
70-180
0-10
Source: Dudney, C.S; Dreibaibis, W.G; Howthon, A.R; Mathews, T.G; Manor, K.P; Quilen,
J.L & Daffron, C.R. Proc. of EPA A PCA Symposium on toxic air pollutants.
Raleigh, USA, 1986.
Interior paints used on submarine hull parts or

equipment are mostly solvent-free. However, some decorative paints
contain solvent, which finds its way into the atmosphere. Also the
plasticisers and driers emanate vapours into the environment.
Common chemicals are: benzene, toluene, xylene, naphtha,
methylene chloride, methanol, etc. The Occupational Safety and
Health Administration (OSHA), USA, specifies the maximum
allowable concentration (MAC) for these chemicals over an exposure
period of 8 hr in the ambient atmosphere, but the standards
applicable for indoor spaces are at least 10 times lower (AppendixE).
Furniture polish contains methanol, dinitrobenzene,
trichloroethane, petroleum solvent, and silicone wax. Tile glazing
composition contains polyurethane and other resins. Volatile
vapours release out from either these basic compounds or from
their decomposition products.
The sprays used inside submarine compartments are
deodorant, hair spray, shaving foam, air fresheners, insecticide,
etc. A few of them are listed in Table 2.10.
Table 2.10. Volatile organics released from materials in
submarine
Material
Chemical name
Gas scrubber
Degreaser
Oxidant
Refrigerant
Insecticides spray
Air freshener
Deodorant spray
Shaving foam
Paint
2.11
Monoethanolamine
Carbon tetrachloride, trichloroethylene
Hydrazine, nitric acid
CFC's
Dicarboxamide, toluamide, petroleum solvent
Synthetic fragrance, propylene glycol, ethanol
Synthetic fragrance, aluminium stearate,
isopropyl myristate, triglycerides
Menthol/citral, glycerine, stearic acid
Xylene, hexane, carbon tetrachloride
FOOD COOKING/WARMING
Cooking of food items, as also warming of foods, is a

matter of concern in submarine compartments. Usually, the
submarines are provided with canned foodstuff, but occasionally
the canned foodstuff is taken out and warmed. Even raw food
material is cooked sometimes. These operations contribute to
contamination of cabin air to some extent. Food odours are
25
26
pleasant only in the vicinity of dining place, but their accumulation

in the whole indoor air is undesirable. Some of the chemical
compounds that are regenerated in these processes are
recorded here.
Meat and meat products release dimethyl sulphide,
(CH 3) 2S. This is the resultant decomposition product from
cysteine; an amino acid present in many animal foods, e.g., meat,
pork, venison, etc. Even on boiling cabbage, the same dimethyl
sulphide is produced. Fresh butter smells from diacetyl
(CH3-CO)2, whereas cheese derives its odour from acetyl methyl
carbinol, (CH3-CO-CHOH-CH3) and -methyl mercaptopropionaldehyde. Onions give out diallyl sulphide (C3H5-S)2 and garlic
produces the allyl propyl disulphide compound. Chocolate gets
its odour from traces of indole, while roasted coffee is a complex
blend of many nitrogenic compounds including caffeine. Tallow
consists of palmitates, stearates, oleates and glycerides, which
on heating produce acrolein, a common chemical encountered
in cabin air (Table2.11). Burnt sugar yields a variety of aldehydes
and ketones which have not-so-obnoxious odours 2.
Table 2.11. Physicochemical properties of acrolein
Substances
Quantity (Range)
Chemical formula
CH2 = CH.CHO
Colour
Colourless to yellow liquid
B.P. 52.5 C.
Sp. gr. 0.8427 at 20C
1 ppm
2.328 mg/m3
TLV
0.1 ppm
Odour
Burnt sweet, acid, pungent
It is very difficult to attribute the odour to any single

molecular structural compound. Sometimes the odour is a resultant
of several compounds known as blend. The science of odours is
still being explored even though many breakthrough aspects have
been discovered. The National Research Council (1979) conducted
several studies and concluded that the chemicals produced from
foods have no adverse effects on human health.
Electrical heaters are employed for warming up food
preparations, as this system is free from any mineral oil fuel. The
contaminant generation on account of heater usage in submarine
compartments is practically nil.
2.12
CIGARETTE SMOKING
Cigarette smoking leads to accumulation of nicotine,

carbon monoxide and particulate matter in the cabin spaces. The
quantities of chemical substances produced on smoking cigarette
in indoor atmosphere are shown in Table 2.1216. It is noteworthy
that even passive smoking, i.e., smoke affecting the persons in the
vicinity, is also hazardous17,18.
Table 2.12. Chemical substances produced by tobacco smoke in
indoor spaces
Substance
Quantity (range) g/m3)
Nicotine
6-50
Pyrrolidine
2-Methyl pyrrole
2-Methyl propyl cyanate
0-5
Heavy metals
Fe
8-15
Cr
1-4
Zn
0-0.5
Pb
0-2
Cd, Ni
Traces
REFERENCES
1.
2.
3.
4.
5.
6.
Wark, K. & Warner, C.F. Air Pollution its origin and control.
Harper & Row Publishers, New York, 1976. p. 6.
Beat, Meyer. Comfort and climate. In Indoor air quality
(Chapter3). AddisonWesley Publishing Co. Inc.,
Massachusetts, 1983. pp. 29-36.
Johnson, R.E. & Sargent, F. The physical and chemical
properties of human sweat and factors affecting the water
balance in confined spaces. Urbana, IL, Illinois Univ. In Beat
Meyer, Indoor air quality, Addison Wesley Publishing Co. Inc.,
Ma, 1968. p. 94.
Morris, J.E.W. & Fallon, R.J. Studies on the microbial flora
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Crennel, J.T. & Milligan, A.G. The use of antimonial lead for
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Martin, T.; Leppard, C.J. & Stickland, R.J.R. Submarine air
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7.
8.
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10.
11.
12.
13.
14.
15.
16.
17.
18.
purification equipment. Presented at Symposium on Naval

Submarines, IKL, London (unpublished), 1983.
Clark, A.N. Air purification in conventional submarines.
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Ramaswamy, V. & Rajan, J.V. Refrigerant gas in low
temperature processes. Chemical Industry Digest, 3rd
quarter issue, 1990, 87-92.
Tillin, A.J. CFCS. The Royal Navy and the ozone layer. J. Naval
Engg, 1990, 32 (2), 232-33.
Bruty, R.A. Oxygen candlesrecent developments. J. Naval
Engg, 1987, 29(2), 412-14.
Mausteller, J.W. Oxygen generation systems. Encyclopedia of
Chem. Tech. 1975, 16, 673-83. John Wiley & Co., New York.
Manual on indoor air quality. Prepared by Lawrence Berkley
Laboratory, Ca, USA, 1984, 4, 3. EPRI, EM-3469.
Girman, J.R.; Hodgson, A.T. & Newton, A.S. Emissions of
VOC's from adhesives with indoor application. Environ
International, 1986, 12, 312-21.
Lebret, E. VOC's in Dutch homes. Environ International, 1986,
12, 323-32.
Knoppel, H. & Setauenberg, H. Screening of household
products for the emission of VOC's. Environ International,
1989, 15, 413-18.
Steadman, R.L. The chemical composition of tobacco and
smoke, Chem. Revs, 1968, 68(2), 153.
Charlyne, W. Bayer, & Manilyne, S. Black. Passive smoking
analysis of office areas vs climate chamber studies. Proc. EPAAPCA Symposium on Measurement of Toxic Air Pollutants, US
EPA, Raleigh, 1986. pp. 25-29.
Hammond, S.K. A method to measure exposure to passive
smoking. Proc. EPA-APCA symposium on measurement of toxic
air pollutants. US-EPA, Raleigh, 1986. pp. 16-24.
CHAPTER 3
POLLUTANTS IN SUBMARINE
COMPARTMENTS
The environment inside the submarine compartments
is of confined type. Men working in this space perform welldefined activities, which determine the extent of pollution and
quality of air in the submarine. The extent of carbon dioxide
liberated inside the submarine is directly dependent on the men.
In addition, human metabolic activity creates organic compounds
through sweat, saliva, urine and faeces. Scales are also generated
from the skin. The machinery meant for driving motors also
produce pollutants. The materials used in anti-pollution measures
spill over and cause damage. The processes namely cooking,
burning of organic materials, firefighting, escape mechanism, etc.
also expel small quantities of vapours, which are notified as
pollutants. On the whole, the management of indoor air pollution
in submarine compartments is an optimisation of several
parameters to minimise the pollution.
In Chapter 2, a detailed account has been given on the
various processes, which generate pollutants in the cabins. As
already observed from the literature, the indoor air pollutants
are in more concentration when the submarine is dived than
when it sails on surface or is at periscope depth. The diesel oil
when consumed in the engines generate carbon monoxide,
carbon dioxide, sulphur oxides and hydrocarbons. The detailed
composition of diesel-burnt exhaust gas mixture is recorded in
Table 3.11. Even though the engine room of the submarine has
well-protected gaskets, which will not allow any of the exhaust
gases to enter the compartments, slight penetration of the
volatile vapours, carbon monoxide, and carbon dioxide takes
place and this will build-up a load of pollutants in the cabin air.
The effect of these pollutants will not be very significant as the
air exchange takes place with outside air, because the
30
submarine is either on surface or snorkel, and ventilation cycle

would be on. However, when the submarine dives underwater,
the batteries render power to drive the electrical motors, and
under these conditions, the displacement of cabin air with fresh
outside air does not take place. The gases generated in a variety
of processes inside submarine are to be controlled by air
purification alone. Common amongst the gases and vapours are;
hydrogen, stibine, sulphuric acid aerosol, carbon dioxide,
organic compounds generated from men at work, freons,
chlorine, hydrogen chloride, odours and microbes. The literature
on the pollutants inside submarine compartments is scanty. Also,
not many predictive studies, modelling, etc. have been made on
the environment in submarines. An effort has been put to bring
out all the existing literature in one chapter and also to illustrate
the usefulness of modelling of pollutants.
Table 3.1 Diesel exhaust gas composition of an automobile
Compounds
Structure
Content
(per cent)
Methane hydrocarbons
Hydrocarbons
CH4, C2H6, C3H8 18.42
C4H10, C5H12
Ethylene
H 2C=CH 2
Acetylene
Carbon
monooxide
Method of
measurement
(approx.)
cryscopic condensation, GC
21.65
HCCH
5.90
CO
0.78
detector tube
Aromatics
6.4
detector tube
Sulphur dioxide
SO2
1.06
p-rosaniline
Source: Seifert JH, 1975.
3.1
CARBON MONOXIDE
Carbon monoxide (CO) is the main pollutant in the
indoor spaces and is generated on incomplete combustion of the
organic materials in fuel-rich flames. Any engine exhaust
contains this gas. The gas has following properties2-4:
Colourless, odourless gas
Poisonous and flammable in air
Boiling point = 7C
Solubility in water (100 ml) = 0.0044 g
Indoor-outdoor measurements were done and many
correlations and models developed. Some of the noteworthy
Pollutants in Submarine Compartments
observations are listed here:
In the air of an ice-skating rink, where an internal combustion

engine operates indoors, the observed level of this gas is as
high as 250 ppm
In commercial and military aircraft, the level ranges from
3-5 ppm
In a school bus, with improper ventilation, the level was
around 3 ppm, and
In an underground garage, the level was 140 ppm.
All these observations point to the fact that carbon

monoxide definitely contaminates indoor spaces where proper
ventilation does not exist5. Carbon monoxide is one of the gases
which was modelled in most environments. One such model
developed for automobiles by Jaeger (1981) and Off (1981) is
pertinent in this connection. The model derives an equation
C(car) = (TDC2(t)/dt) + C2(t)
where T is the time constant, which depends on the window position
and the speed of the car, i.e., a typical figure 45 minutes for a
closed car with one window at drivers side only one-third open.
Further, designer of the model states, that the level of carbon dioxide
depends on the strength of source, ventilation rate and residence
time.
3.2
CARBON DIOXIDE
Carbon dioxide (CO2) is a dense gas generated from

human metabolic activity. It is a colourless, odourless gas with
slight acidic taste. The gas is partially soluble in water, i.e.,
0.348g/100 ml water and has a gas density of 1.976 g/l (at 0C) 6.
Its concentration in the environment has direct correlation to the
number of men at work and the period they remain in the closed
chambers. The gas level of occupied rooms is always higher than
the outdoor atmospheric levels. The concentration of CO2 follows
a diurnal pattern in any enclosed space, as the work of men goes
on. The quantity of CO2 generated per man per hour in the
enclosed space of submarine has been taken as 25 litres and
based on this, the total gas generated by n men is
C = n 25
31
32
where C is the total carbon dioxide generated per hour. It is thus

possible to calculate the total gas produced by men in the
submarine and also predict the level of the gas in the compartment
air from time to time. The management of CO2 in both fleet and
nuclear submarines is an important aspect.
3.3
HYDROGEN
Each cell functioning in the submarine battery pit
generates hydrogen gas at the negative plates during discharging
and charging operations. Hydrogen is a light gas and has two
isotopes, namely, deuterium and tritium 7. Although hydrogen is
not a toxic gas, it is hazardous in nature by causing explosions.
The quantum of gas generated during the discharge in a
submarine can be calculated from the equation
VH2 = VH 2 (Ah) K n F
where VH2 (Ah) is the volume of gas generated per ampere hour,
which progressively increases with increase in the ampere hours,
F is a constant = 5, n is the number of cells, and K is capacity. On
the whole, monitoring of hydrogen on board during sailing is
mandatory.
3.4
STIBINE
Stibine is another noxious gas found during the discharge
of cells in the battery pit of a submarine. It is a colourless and
poisonous gas with disagreeable odour. It is sparingly soluble in
water8. The plates of a lead acid battery contain 7-10 per cent of
antimony and this metal affords toughness to the plate. When the
cell is discharging, sufficient quantity of hydrogen generates at the
cathode end and a portion of this gas reacts instantaneously with
antimony metal producing antimony hydride (SbH3, otherwise known
as stibine). It was demonstrated that during each charge of battery,
antimony metal from the positive grid is deposited (in minute
quantities) over the negative plate; and this deposited metal has
high reactivity. Old plates contain more active metal of antimony
than new plates, and are therefore, subject to serious local action
resulting in the formation of stibine. High current density and high
density of sulphuric acid facilitate the formation of stibine.
3.5
SULPHURIC ACID AEROSOL

Concentrated sulphuric acid (sp. gr. 1.83) is slightly
diluted with water to a sp. gr. of 1.3 and used as the electrolyte for
batteries. Due to the rolling and pitching of submarine, small

droplets of the sulphuric acid spill out and get sprayed in the air in
battery compartments. The resultant sulphuric acid aerosol,
having a particle size ranging between 0.1-0.5 m is a pollutant in
the cabin space. The residence time of the aerosol is considerable
and the concentration of acid in air depends upon the motion of
the submarine. Being a heavy aerosol, the spray is restricted to
the battery pits only. Monitoring of sulphuric acid spray in the
battery compartment is essential from the safety point of view.
3.6
OXIDES OF SULPHUR & NITROGEN

Sulphur oxides, mainly sulphur dioxide and sulphur
trioxide are generated during combustion of any sulphur-containing
fuel. The emitted sulphur oxides reside in the atmosphere for long
time and then are deposited on the ground. In a submarine, this
gas is produced from the low sulphur diesel oil (0.5 per cent and
below), which is adapted as the fuel in the engines.
In the same manner, the combustion process affords
nitrogen oxides. At the temperature of the flame, oxygen and
nitrogen combine together to produce nitrogen oxide, which later
on transforms into NO2 and gives rise to NOx (95 per cent NO and 5
per cent NO2). Both sulphur dioxide and nitrogen oxide react with
indoor formaldehyde and reduce the organic pollution.
3.7
ORGANICS
As discussed in Chapter 2, the organic substances
in the submarine compartments are generated mostly from
human metabolic activity and their quantity is proportional to
the number of persons residing. Table 2.3 lists the most common
organics found in submarine compartments and their average
concentration levels.
Cooking of food items, such as meat, tallow, garlic, etc.
in the galley space produces a number of organic substances.
Paints, polishes, panels, freons and MEA scrubbers also
contribute to the loading of organic chemicals in the closed
environment of submarines. In addition, smoking of cigarettes
contribute a variety of organic compounds, of which the
polynuclear aromatic hydrocarbons, -Benzopyrene is the most
toxic. The composition of tobacco smoke is shown in Table 2.12.
3.7.1

A variety of organic compounds whose structures are
based on polycyclic aromatic rings are isolated from the
33
34
Figure 3.1. Pyrosynthesis pathway for benzo--pyrene
combustion products of wood, fuels, organic wastes and tobacco

smoke. These complex compounds are generated through a
process known as pyrosynthesis (Fig. 3.1). All these compounds
are carcinogenic in nature and if inhaled by men may produce
cancer and similar ailments (Table 3.2).
There are two pyrosynthesis pathways. Firstly, at high
temperatures above 400-500C, organic compounds burn
incompletely and crack down into lower fragments. Secondly,
the fragments recombine through free radical mechanisms to
yield a thermodynamically stable polynuclear aromatic
hydrocarbons. The equations shown in Fig. 3.1 broadly explain
the mechanisms.

Table 3.2. Important polynuclear aromatic hydrocarbons, their
average concentrations and carcinogenicity
Structure
Carcinogenicity
Concentration & source (mg/1000 m3 )
Benzo--pyrene
+++
5.7
20-39
96 ppm
USA (average)
London street
Cigarette smoke
Benzo--anthracene
~4
USA (average)
Benzo-e-pyrene
5
12-26
USA (average)
London street
Perylene
0.7
USA (average)
Benzo-j-fluoranthrene
++
0.8-44
USA (average)
Benzo-k-fluoranthrene
1.1-20
USA (average)
Source: Beat Meyer, 1983.
3.7.2
Hydrocarbons
Organic compounds of aliphatic and aromatic types are
termed as hydrocarbons and these generate from fuel burning.
Methane is found in natural swamps and can enter the submarine
environment during usual air exchanges. Besides, refinery
chemicals, such as butane, propane, and octane can enter the
enclosed spaces through cooking gas or engine room. In addition,
the decomposition products of diesel combustion contain a variety
of aliphatic and aromatic hydrocarbons. The decomposition
compounds arising from diesel combustion have already been
outlined in Table 3.1.
3.8
HYDRAZINE
The submarine carries hydrazine in shells. When

admixed with an oxidant, usually nitric acid, nitrogen gas is
spontaneously liberated and this gas expels the water in ballast
tanks so rapidly that the submarine is brought up from even a great
depth. The indoor spaces get contaminated with vapours of
hydrazine during this operation. Hydrazine has ammoniacal odour
and is carcinogenic and has boiling point 113C, sp. gr. 1.01 and
vapour pressure (16 mm at 20C). 1 ppm = 1.33 mg/m3.
3.9
MONOETHANOLAMINE
The scrubbers employed for absorbing carbon dioxide use

monoethanolamine (MEA) as the reactant. MEA has the
characteristics shown in Table 2.5 (Chapter 2). During air
revitalisation process, the vapours of MEA enter the cabin and
35
36
contaminate the air. It is therefore necessary to monitor MEA in

compartments when submarine dives underwater.
3.10
CHLORINE
Chlorine finds its way in submarine compartments when a
peroxide candle is lighted. It arises from the potassium chlorate,
which is a constituent of the oxygen candle. Slight amount of chlorine
is also generated from the decomposition of freons at hot surfaces in
the submarine. Chlorine is a heavy gas having density of 3.214 g/l at
0C/1atm. Its boiling point is 34.6 at 1 atm and is fairly soluble in
water to the extent 14.6 g/l (1 ppm = 2.90 mg/m3). It is toxic in nature.
3.11
MICROBES
The environment in submarines is prone to the growth of
airborne microbes. The sneezes produce particulates of 110 and
dissipate them to distances upto 1 m. Microbes from timber parts,
air-conditioners, carpets, human skin scales and foodstuffs also
generate several particulates. Indoor organisms, Aspergillus
fulminates, can cause asthma at a temperature ranging from 20 to
50C and can infect the sailors. Old books, rags, canvas, etc., in
cupboards also grow the allergens in submarine compartments.
Proper control of humidity, temperature and ventilation would
minimise the production of microbes in enclosed spaces4.
REFERENCES
1.
2.
3.
4.
5.
6
7.
8.
Seifert, J.H. Air pollution. McGraw Hill Book Co., New York,
1975. pp. 359-66.
Charles, M.; Bartish, & Drissel, G.M. Encyclopaedia of chemical
technology. John Wiley and Sons, NY, 1978. Vol 4, pp. 772-93.
Charles, D. H. Handbook of chemistry & physics. 36th edn.
Chemical Rubber Publishing Co., Cleveland, USA, 1954.
Dean, J.A. Lang's handbook of chemistry. 12th Edn. McGraw Hill
Book Co., New York, 1979, p. 4-38.
Beat Meyer. Indoor air quality In Comfort and climate
(Chapter3). Addison-Wesley Publishing Co. Inc.,
Massachusetts, 1983. pp. 29-36.
Ballon, W.R. Carbon dioxide In Encyclopaedia of chemical
technology. John Wiley & Sons, New York, 1978. Vol 4,
pp.725-40.
Mandelik, B.G. & Newsome, B.G. ibid, 1978, Vol 12, p. 938.
Freedman, L.D; Dock, G.O, & Long, G.G. Stibine, ibid, 1978,
Vol 3, p. 106.
CHAPTER 4
EXPOSURE TO INDOOR POLLUTANTS &
HEALTH EFFECTS
The term exposure refers to the physical contact of the
pollutant to human body. The concentrations of the pollutant(s)
are known as exposure levels and the duration of contact, the
exposure period. Another term, dose is understood as a multiple
of concentration and period and this figure gives a definite mass
of pollutant, which has been ingested into the human body of a
particular body weight. All these terms give meaningful
interpretation of the indoor air pollution activity, especially as
regards to environment in submarine.
It is very important that the indoor air should be fit for
inhalation by any category of persons, such as young, old,
infants and individuals with hypersensitivities, allergies or
idiosyncratic responses to substances, etc. Even though strong
and healthy men are taken for work on board submarines, care
should be taken that pollutants coming in contact with organs
such as heart, lungs, kidneys, etc. do not cause damage during
the cruising operations.
The short-term and long-term effects of pollutants
on human beings have been studied extensively and good
correlations were obtained. It has been concluded that
short-term exposure to certain indoor air pollutants in high
concentration may become more serious than long-term
exposure to the same pollutant in moderate concentration.
Indoor pollution has to be recognised as different from
outdoor (ambient) pollution as the former is more localised
and governed by several man-activities. As regards air
pollution at workplaces, mostly indoors, the types of
pollutants are known, and their behaviour is also well
understood by the subjects. The persons who are exposed to
these pollutants are also aware of the precautions to be
38
followed in case of exposures. All possible methods are adopted

for the control of pollutants at source itself in case of
workplaces/indoors.
Moreover,
short-term
studies
are
conducted at workplaces/indoors over a duration of 8 hrs and
long-term studies over many years (with an average of 24hrs).
This chapter discusses the exposure levels of pollutants in
indoor environment, the health effects caused by single
pollutant, the synergistic effects and the evolution of safe
levels for exposure 1-3.
4.1
CARBON MONOXIDE
The exposure of men to carbon monoxide differs from
place to place (Table 4.1), where the type of activity is different;
for e.g., in enclosed kitchens, the range of carbon monoxide
concentration is between 5-50 ppm, in restaurants about 40ppm;
in enclosed ice skating rink where a diesel engine operates, it is
between 45-250 ppm; in cars 20-35 ppm; and in submarines 8-35
ppm. Several studies have shown a good correlation between
carbon monoxide generation and diesel/cigarette burning
process.
Carbon monoxide enters the human body through
respiratory system and reacts immediately with haemoglobin of
the blood stream forming carboxyhaemoglobin. The affinity of
carbon monoxide to haemoglobin is 240 times more than that of
oxygen itself and hence gets preferentially absorbed forming
carboxyhaemoglobin (COHb) and blocking further entry of oxygen.
The reversal process of obtaining haemoglobin is rather slow.
Carboxyhaemoglobin levels beyond 4 per cent are undesirable.
Smokers inhale carbon monoxide considerably and maintain
COHb level beyond 4 per cent invariably, whereas nonsmokers
when exposed to 50 ppm of carbon monoxide for 90 min develop a
level of COHb to the extent of 2.5 per cent in the blood. A level of
COHb above 5 per cent will bring in pulmonary and cardiac
changes in men.
Table 4.1. Effects of exposure of carbon monoxide on men
Concentration
of CO (ppm)
15
30
100
Concentration
of COHb
(per cent)
3
4
15
Duration of
exposure
(hrs)
8
3
2.5
300
40
600
80
Symptoms
None
Slight headache
Headache,
reduced mental
activity
Throbbing
headache
Coma (fatal)
Effects
Nil
Irritation
Poor
performance
Restlessness
Total breakdown
Exposure to Indoor Pollutants & Health Effects
4.2
CARBON DIOXIDE
The physiological effects of carbon dioxide on men,

exhaled and passed into the closed environment of submarines,
has been thoroughly investigated by Schaefer4 in 1968. Natural
air contains carbon dioxide to the extent of 300 ppm (0.03 per
cent) and this renders greenhouse effect in the atmosphere. In
enclosed spaces, such as submarines, spacecraft, subways,
tunnels, theatres and classrooms, much higher levels of carbon
dioxide have been registered.
Carbon dioxide causes acidosis in men and this is
indicated by many parameters, such as pH, carbon dioxide
release, bicarbonate and electrolytes levels. The physical
changes that occur are pulse rate, blood pressure, etc. The carbon
dioxide adaptation in human body in different concentrations is
shown here.
Concentration
(per cent)
Extent of physiological
change
0.50.8
No serious change
Normal behaviour
1.01.5
Tendency
Abnormal behaviour which
1.0 and above
towards
Effects
change
will revert to normalcy later
Functions disabled
Performance deterioration and

permanent damage
From these three categories, to draw a specification for

maximum allowable concentration (MAC), the measurement of
basic physiological functions and standard performance tests
alone can not be considered adequate, since a person exposed to
1.5 per cent level of carbon dioxide takes 23 days of adaptive
process in a submarine and thereupon, on release from the
atmosphere of carbon dioxide, he takes more than 28 days to
come to normal condition. Therefore, the third level, namely,
0.5-0.8 per cent V/V for carbon dioxide where no adaptation
processes take place has been chosen as the MAC for carbon
dioxide4.
4.3
OXIDES OF SULPHUR & NITROGEN
Sulphur dioxide is a pungent gas and causes

respiratory disorders, such as bronchitis, emphysema and
asthma. It also causes irritation to eyes. Many epidemiological
studies have been conducted on exposure of men in indoor spaces
39
40
to sulphur dioxide and the MAC has been fixed at 5 ppm for
ambient air. For indoor environment the MAC has been reduced
by a factor of 100.
Amongst the oxides of nitrogen present in air, nitrogen
dioxide and nitric oxide are the most stable. Nitrogen dioxide
causes irritation to eyes and nose at concentrations beyond
10ppm. Increased levels beyond 200 ppm of nitrogen dioxide
produce pulmonary oedema in men5, 6.
4.4
SULPHURIC ACID AEROSOL

Overexposure to sulphuric acid will result in
bronchitis, pulmonary oedema and other respiratory diseases.
The physiological responses are related to the aerosol particle
size and concentration. The aerosol particle size has been
observed to be in the range of 0.5-2 inside the battery
compartment and the concentration around 200 g/m3. The
MAC for sulphuric acid aerosol is, 0.1 mg/m3 of air as laid down
by ACGIH, OSHA and NIOSH, USA. The following are some of the
effects when high concentrations of sulphuric acid are
encountered in the indoor environment/workplaces 7:
Concentration of sulphuric acid
(mg/m3)
4.5
Response
0.52.0
Irritation, coughing are easily noticeable
3.04.0
Decidedly unpleasant
6.08.0
Marked alterations in respiration.
STIBINE
Stibine is antimony hydride produced during battery

charging and discharging operations in submarines. It is a nerve
toxin at concentrations above 1 ppm8.
4.6
CHLORINE
Inhalation of chlorine continuously results in cough,

pulmonary oedema, pneumonia, tracheobronchitis and burning
of eyes. Chlorine also attacks the mucous membrane. The safe
concentration of chlorine is 1 ppm9.
4.7
HYDRAZINE
Hydrazine is a liquid which passes through skin and

cause dermatitis. It also irritates lung, liver and kidneys;
prolonged contact of hydrazine causes cancer10.
4.8
ORGANICS
The prevalence of organic compounds indoor is more

than in open atmosphere11. Firstly, the organics are generated
from human metabolic activity and are retained in the enclosed
spaces. Secondly, some of the utility products, such as paints,
polishes, MEA, formaldehyde, cooking gas, freons, etc. leave
vapours in the indoor environment. Surrounding the habitants,
these chemicals cause skin diseases, allergies and irritation to
eyes. Aromatic hydrocarbons of the benzopyrene type are even
carcinogenic. Freons and halocarbons on decomposition at hot
surfaces emit hydrogen chloride, which is pungent and irritative
to skin12.
4.9
SYNERGISTIC EFFECTS
Since many pollutants coexist in the indoor

environment at any given time, it is necessary to understand the
synergistic effects caused by other pollutants on the notified
pollutant. The synergism is studied extensively for ambient
atmospheric pollutants; however, in indoor environment, due to
the non-convective movement of air, there exists a situation
wherein the pollutants may react with each other leading to a
complex mixture (a situation similar to photochemical smog
formation). La Belle, et al reported that the synergistic effects of
mixed gases/vapours are more pronounced and greater than the
effects displayed by individual components. An empirical equation
developed to measure the effect of individual pollutants in a
mixture on men is given as:
{Ci /S MAC i } = 1
(4.1)
where i is a toxicological group of n contaminants, SMAC is the

maximum allowable concentration based on toxicity, and C is the
maximum allowable concentration of each contaminant in the
mixture. From this, it follows that for a contaminant X
(MAC=20ppm) and another contaminant Y ( MAC = 40 ppm) are
present in air at the same time and are limited to concentrations
of 15ppm for X and 10 ppm for Y respectively, then Eqn. 4.1
becomes:
{Ci /SMAC i } = 15/20 + 10/40 = 1
(4.2)
It is thus logical that the individual MAC for X has to be

reduced to three-fourths of existing MAC and that for Y has to be
reduced to one-fourth of existing MAC when these two
41
42
contaminants coexist in the mixture. The synergistic effect of one

on another is thus very much pronounced13.
Practically all gases act as synergists with carbon
monoxide, for example, nitrogen dioxide of 250 ppm and hydrogen
sulphide of 400 ppm will act as synergists. Sulphuric acid aerosol
synergises sulphur dioxide and causes visible injury to lungs in
human beings. Cigarette smoke contains a variety of chemical
substances, such as oxides of nitrogen, formaldehyde, benzopyrene,
carbon monoxide, carbon dioxide, aliphatic and aromatic
hydrocarbons and lead particulates, which all act as synergists to
carbon monoxide (around a concentration of 400ppm) and bring
immense health hazards in men within 5 min.
4.10
EFFECT OF INDOOR AIR POLLUTION IN

SUBMARINE
The air pollutants which require serious attention
inside the submarine compartments are: carbon monoxide,
carbon dioxide, chlorine, stibine, aerosol of sulphuric acid,
hydrazine, nitrogen oxides, organics, and particulates of both
inorganic and microbe types. Each of these pollutants, if exposed
to men for a long duration causes several metabolic changes
leading to illness.
The entry of many gaseous and particulate pollutants
into human body is through the respiratory tract as well as
contact of skin. On finding a place in the body, the individual
pollutant reacts with the enzyme systems and manifests
functional disorders. On many occasions, the pollutants show
synergistic action also, e.g., cigarette smoke pollutants on human
body, or the particulate matter carrying the adhered metals or
organic materials.
4.10.1
(a)
(b)
Remedies
Carbon monoxide poisoning can be treated by reversing the

conversion of COHb to Hb on exposure to pure ambient air
for over a period of 2 hrs. During this period the reversal
takes place and the effects of inhalation of poisonous gas is
nullified. Timely rescue of the person and strict medical
supervision are needed.
Persons suffering from acidosis, i.e. exposure to carbon
dioxide may be treated in similar manner as above. In
addition, administering diuretics would restore the pH
balance in the blood system of human body faster.
Chlorine, NOx and acid aerosol enter the body through

nostrils and first damage the mucous membrane. An
antibiotic paraffin-based ointment if applied in the nostrils
renders relief. Similarly, medicinal eye drops relieve the
pain. Very severe damages to organs have to be treated
under medical supervision.
(d)
Particulates are of two types: (i) Particulates whether
inorganic or organic having a single constituent, e.g.,
metals, organics, cotton, asbestos, silica, etc. and (ii)
Particulate matter with several absorbed toxic liquids or
gases in it, e.g. carbon with aerosol of sulphuric acid, or
stibine vapour. The second category is more dangerous. Any
particulate below 0.5 diameter travels through the nose
and reaches the lung (alveoli) and settles down there. Its
removal is rather difficult. Particulates of diameters 0.5-5
get filtered at intermediate places. The inorganic poisonous
particulates are lead, iron, antimony, arsenic, cadmium and
mercury either as metals, oxides or organo-metallics.
Organic particles, such as benzo-pyrenes and carbon dust
are extremely toxic since these carry other pollutants too
along with them14.
The damage caused by these pollutants to human body
are both short-term and long-term; bronchitis, allergy, oedema
and angina, etc. are immediate, whereas carcinogenicity is a
long-term effect15. Even microbes and pollen dust in air cause
similar effects in men.
(c)
The treatment of short-term diseases, such as

bronchitis and oedema is through medication. The toxic effects
caused by organic carcinogens require careful attention at this
stage. It is learnt that about 90 per cent of the organic
substances produced in the burning of coal, oil, paper, wood, etc.
produce degradation products, which are carcinogenic to human
body. The effects in men are shown slowly, depending on the body
metabolism; and these are due to the destruction of enzymes,
such as arylhydrocarbon hydroxylase (AHH), etc.
Benzo-pyrenes, N-Nitroso compounds, dimethyl benzo-lanthracene (DMBA), polychlorobenzenes (PCB), DDT residues,
hydrazine, azo dyes, gasoline, rocket propellents and some coal
tar products cause ill-effects. Skin cancer is very common and
tumours affecting other parts of body besides liver and kidney.
The symptoms are dizziness, convulsions, dermatitis, nervous
disorders, hepatitis, atherosclerosis, oedema and degeneration of
olfactory functions.
43
44
Dietary supplementation of protein, vitamins and

minerals reduce some of the effects, e.g.,
administering iron
through diet in human body reduces the cadmium-induced
anaemia. Use of magnesium rich diet influences the
mobilisation of lead in the body. Calcium in diet checks the ill
effect caused by chlorinated hydrocarbons absorption. Vitamin A
helps in reducing the symptoms of toxicity caused by PCBs, DDT,
dieldrin, heptachlor, etc. and plays a key role in stabilising the
functions of tissues of retina, liver, etc. Liver cirrhosis,
hepatotoxicity caused by pollutants are satisfactorily treated by
administering riboflavin. Even benzo-o-pyrene-induced tumours
are treated with this vitamin. Cyanocobalamine, B 12 is useful
for the treatment of toxicity-induced by tobacco smoke and carbon
disulphide. VitaminC is a general detoxicant for a wide variety of
toxic chemicals of both heavy metals and chlorinated aromatics,
benzo-pyrenes. It has been demonstrated that dietary protein
(caesin 4 per cent) reduces hepatotoxicity caused by lead,
selenium and even chlorinated organics. Finally, a category of
anti-carcinogens reported are:
(i)
Disulfiram and related compounds which inhibit the toxic

effect of DMH-1, 2-dimethyl hydrazine-induced cancer,
(ii)
Phenolic antioxidants such as butylated hydroxy anisole
(BHA) and butylated hydroxy toluene (BHT),
(iii) Flavones, e.g. 5, 6-benzo-l-flavone (BNF), quercetin, rutin,
and,
(iv) Indoles, e.g. Indole 3-carbinol, 3, 3-diindole methane, indole3-acetonitrile.
It is interesting to note that some natural plant
colouring materials and foods (such as cabbage, cauliflower,
broccoli, and brussel sprouts) contain these anti-carcinogenic
substances. It is thus possible to include these foodstuffs in the
diet of submariners to prevent the onset of a long-term effect.
4.11
RISK ASSESSMENT
Nearly all contaminants generated in the confined
spaces of submarines are injurious to the personnel working in
the ship and manifest ill effects in health. Therefore, risk
assessment on the adverse consequences of exposure to these
indoor contaminants has assumed great importance. The
essential facets of risk assessment are:
Hazard identification
Dose response assessment
Exposure assessment, and
Risk characterisation
Hazard identification pinpoints whether any particular

chemical is the determining factor for causing health symptoms.
Dose response assessment deals with the relationship of
magnitude of exposure to pollutant and the probability of
occurrence of health effects.
Exposure assessment and risk characterisation
establish the extent of human exposure and the resulting type
of risk that has set in. Thus, the risk of contracting an air
pollution-related injury to man working indoors of a submarine
mainly depends on the exposure level, duration and physical
characteristics of pollutants, i.e. mode of transmission, physical
body weight, ventilation, mode of penetration, health of person,
age, etc. Risk assessment also allows a comparison of risks for
alternate options, such as the risk of inhaling high concentration
of carbon dioxide in air for short duration is less than that of
breathing the same in moderate concentration for longer time.
The adaptation or the time to reach compensation of respiratory
acidosis in human beings is about six days when carbon dioxide
level remained at 3 per cent in air and the adaptation to carbon
dioxide levels of 1.5 per cent in air remain over a very long
period (26 days).
4.11.1
Role of Risk Assessment in Submarine

Environment
When a submarine dives underwater, environment in
the compartments is of confined type. Air entry or exit does not
take place. Men inside exhale carbon dioxide during breathing
from the available air. The concentration of carbon dioxide in
fresh ambient air is 0.03 per cent. After approximately 7 hrs of
continuous diving its concentration reaches 1.0 per cent. It can
be seen from the foregoing chapter that the tolerance for human
body to carbon dioxide exposure above 1 per cent level is not
much. Therefore, in submarines a short term risk is foreseen on
account of carbon dioxide exposure, in case it is not absorbed or
eliminated. Schaefer studied the dose-response relationship in
men and developed a time-concentration curve for adaptation to
carbon dioxide. According to this, it is seen that a dose of carbon
dioxide at 3 per cent over six days can bring chronic toxicity in
men, but a concentration of 1.5 per cent can be tolerated for
26days with slight health effects.
The health hazards displayed on exposure to chlorine,
stibine and sulphuric acid aerosol in submarines are not very
significant when the duration of exposure is short and the
concentration of these substances are low 3.
45
46
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
Wark, K. & Warner, C.F. Air pollutionits origin and control.

Harper & Row Publishers, New York, 1976, p. 6.
Carbon monoxide. Environmental Health Criteria
No. 13,
1979; No. 4, Oxides of nitrogen; 1977; No. 54, Ammonia, 1986;
No. 8, Sulphur dioxide, 1979. World Health Organisation,
Geneva.
Clayton, G.D.; Clayton, E.F. Air pollution (Chapter 14). In
Pattys industrial hygiene & toxicology, Vol. 4 (3rd Edn). John
Wiley & Sons, New York, 1978. pp. 595-52.
Schaefer, K.E. A concept of triple tolerance limits based on
chronic carbon dioxide toxicity studies. Aerospace Medicine,
1961, 32, 197-204.
Sulphur dioxide. Environmental health criteria. No. 8. World
Health Organisation, Geneva, 1979.
Health consequences of sulphur oxide.
Environmental
Protection Agency (EPA), USA, 1974. 650/1-74-004.
Kirk-Othmer. Sulphuric acid In Encyclopaedia of chemical
technology, Vol. 22. John Wiley & Sons, New York, 1983.
pp.229.
Schaefer, K.E. Environmental physicology of submarines and
spacecraft. Archieves of Environmental Health, 1964, 9, 320331.
Chlorine and
hydrogen chloride. Environmental health
criteria. No. 21. World Health Organisation, Geneva, 1982.
Hydrazine. Environmental health criteria No. 68. World
Health Organisation, Geneva, 1987.
Scott, B.W. & Stuart, J.H. Atmospheric contaminant sensor
book 1; design and fabrication of mass spectrometer for
submarine atmosphere monitoring, Pomana, CA; PerkinElmer Corporation, USA, 1980, pp. 1-14.
Diffen, P.R. & Foulger, B.E. Atmospheric profiling of organic
contaminants in submarinesHuman environment in
submarines. Conference Proceedings of Undersea Defence
Technology, Microwave Exhibitors & Publishes Ltd., UK,
1988. p. 72.
Shrivastava, A.K. & Rao, Koteswara M.V.R. Environment in
submarine compartments. Def. Sci. Jour. 1987, 37(2),
257-67.
Singh, Inderjeet; Sethi, S. & Iqbal, S.A. Environmental
pollution, causes, effects and control. Commonwealth
Publishers, New Delhi, 1992, p. 169.
Ray, P.K. Pollution and health. Wiley Eastern Ltd. New Delhi.
1992, pp 54-59.
CHAPTER 5
DAMAGE TO MATERIALS & EQUIPMENT
Practically all air pollutants condense on the surface of
precious equipment or artistic articles and react with the
material. The concentration of the pollutant, exposure period,
temperature, humidity and diffusivity determines the extent of
damage to the object. The mechanism of reactivity of pollutant
with the constituents on the surfaces is same for ambient and
indoor environment. Some effects caused by indoor pollutants for
materials and equipment are described here.
Carbon dioxide or its hydrate, carbonic acid in high
concentrations embrittle paper, drawings, paintings, photos and
also attack the surface of limestone, sandstone, etc. Acidic
pollutants, such as nitrogen dioxide and sulphur oxides also
behave in the same manner. They react with the construction
materials, namely, iron, aluminium, ceramics and copper. Even
the microprocessors in the control equipment of a submarine are
also succeptible to damage by the acidic pollutants. Hydrogen
sulphide reacts with painted surfaces in submarines and tarnish
them by forming lead sulphide. Coloured panels are decolourised
due to the action of chlorine, ozone and nitrogen dioxide. Rubber
gaskets, O-rings and washers are affected by contact with ozone.
Leather items are equally affected on exposure to the pollutants.
Soot particles in combination with gaseous pollutants first
deposit, adhere strongly and then react with glass and ceramic
parts of electronic equipment in the submarines. Grit or suspended
particulates deposit on gauges of measuring equipment. The
damage caused by mercury vapours to the compass of ships is
noteworthy. Stibine and hydrogen sulphide react with catalysts and
adsorbents
and
reduce
their
effectiveness.
Ammonia,
triethanolamine, monoethanolamine and hydrazine, which enter
the submarine compartments come in contact with the solid
polymer electrolyte of oxygen electrolyser plant and damage the
system. Freons used as refrigerants and halons packed in
48
firefighting cylinders leak into the indoor environment and

convert into hydrogen chloride or hydrogen fluoride at hot surfaces.
These acid fumes corrode the metal, glass and ceramic parts of a
submarine 13.
It is very essential to assess the buildup concentration
of the pollutant in the confined atmosphere for saving the
equipment from damage. The men working in a submarine have
to be taught fully on the type of pollutants and their reactivity
with materials, surfaces and equipment. Since all the pollutants
are not produced in the same compartment and are generated at
different times, appropriate methods should be evolved to
contain them at their originating locations as far as possible.
All drawings maps and documents are to be placed in
storewells. Good packaging of household items, like paints,
polishes, cleaners, also help in containing the organic vapours.
Maintaining good inventory of items that release the vapours, and
publicising the precautions to be taken for arresting the pollution
will help in reducing the damage to materials and equipment in a
submarine.
REFERENCES
1.
2.
3.
Parker, A. Industrial air pollution handbook. McGraw Hill

Book Co., New York, 1978, pp. 5-24.
Stern, A. Air pollution, Vol II, Materials damage. 3rd edn.
Academic Press, New York, 1977, pp. 65-112
Wark, K. & Warner, C.F. Air pollution, its origin and control.
Harper & Row Publishers, New York, 1976. p. 6.
CHAPTER 6
AIR QUALITY STANDARDS IN
SUBMARINES
Air quality standards for submarines help in checking
the extent of pollution in the compartments on account of human
activity and machinery functioning. Generally speaking, these
standards should be more stringent than the regular ambient air
standards or even industrial exposure standards, because of the
typical environment created within the submarine when
underwater. Also, the life support facilities in the submarine
should never be allowed to fail, but always made to function as
per the commands given.
6.1
DEVELOPMENT OF OSHA, ACGIH & SUBMARINE

STANDARDS
The ambient air quality standards enuntiated by the US
Environmental Protection Agency (EPA) are widely used all over the
world as guidelines for maintaining clean ambient environment. The
EPA mandate has been to provide the population, primarily public
health protection, and secondly public welfare and safety. Table6.1
lists the national ambient air quality standards1.
Table 6.1. National ambient air quality standards
Pollutant Time
weighted
average
#
Concentration in ambient air
Industrial Residential Sensitive
area
area
area
Method of
measurement
SO 2
24
120
80
30
West & Gaeke

UV Flourescence
NO X
24
120
80
30
Jacob & Hochheiser,

Gas phase chemiluminescence
SPM
24
500
200
100
High volume sampler
CO
Pb
24
5 mg/m3
2 mg/m3
1 mg/m3 NDIR
1.5
1.0
0.75
#g/m3
Source: Central Pollution Control Board, Government of India.
AAS
50
As regards the industrial environment, the persons

working in these areas are already educated on the exposure of
pollutants and are provided some guarantees of protection. Thus
occupational safety in industry, though very important, can be
achieved with less effort as compared to the public protection in
ambient atmosphere. The US Occupational Safety and Health
Administration (OSHA) has drawn standards pertaining to the
exposure to toxic pollutants in industrial or occupational areas
during the eight-hour period of work (AppendixE). A much more
comprehensive regulation was developed by the American
Conference of Government and Industrial Hygienists (ACGIH) based
on accumulated experience with workers' health and results
obtained in animal experiments through exposure to toxic
substances. The term exposure in this context of health effects
denotes the quantum of toxic gas as well as the period under which
the person is affected. Therefore, these exposures are expressed
as Time Weighted Average (TWA) in industry and all OSHA standards
thus denote TWA for eight-hour exposure. This situation of only
eight-hour exposure per day or forty-hour intermittent exposure per
week at workplace in industry does not apply for residents who live
in indoor environment. Since these persons in enclosed spaces are
constantly exposed to pollutants all through the day, it is imperative
that OSHA standard needs some modification. This has been
achieved by reducing TWA eight-hour of OSHA by a factor of at
least 1/10 for general safety. Present-day submarine air quality
standards are derived on these considerations.
6.2
ADDITIONAL STANDARDS
The Naval Research Laboratorys report2 entitled Limits

and Measuring Methods for Atmospheric Constituents in Nuclear
Submarines deals with the standards that are to be followed (US
Submarine Arm for Protecting the General Health of Crew). A
NATO specification which is similar to the Soviet specification is
also in practice in Europe. Most of the standards are derived from
OSHA regulations, USA, only by applying an additional safety factor.
A civil publication by E.A. Ramskill 3 notifies the
standards for many toxic gases generated in nuclear subsubmarines. Similar publications were made by H.W. Carhart, and
V.R. Piatt4 (1963). The present status of Chemical Research in
Atmospheric Purification and Control in Nuclear Powered Submarines
NRL Washington, Report 6053; Probable Contaminants and their
Recommended Air Levels in Space Vehicles, Boeing Doc.D.2-90731-1.
The Boeing Co, Seattle5, also cover this subject.
Air Quality Standards in Submarines
REFERENCES
1.
2.
3.
4.
5.
Central Pollution Control Board, Govt. of India. 1994.

Limits and measuring methods for atmospheric constituents
in nuclear submarines. 1970. Naval Research Laboratory
Report No. NAVSEA 0938. 011-4010, Rev B.
Ramskill, E.A. Nuclear submarine habitability. Society of
Automotive Engineers, Mat. Aeronautic Meeting, 351, D,
1961.
Carhart, H.W. & Piatt, V.R. The present status of chemical
research in atmospheric purification and control in nuclear
powered submarines. NRL, Washington, Report No. 6053,
1963.
Probable contaminants and their recommended air levels
in space vehicles. The Boeing Co., Seattle, USA. Boeing DoC.
D.2-907311.
51
CHAPTER 7
AIR POLLUTION MODELLING IN
SUBMARINES
The indoor air pollution models developed routinely for
closed homes are mathematical expressions that yield predictions
of pollutant's concentration in specific situation and the same will
hold good for submarine compartments too1. These models are
useful for calculating the emissions of gases and vapours indoors
and to establish the concentrations at any given time. This will
help in triggering eliminator systems which operate in submarines.
7.1
MASS-BALANCE EQUATION
The basic hypothesis for modelling indoor air quality is
the Mass-Balance equation, i.e.,
Accumulation = Rate of [Input + generation
(output + sink)]
Rate which is represented as
V.dCin/dt = Rate of change in mass {(Infiltration of
indoor air) + (Generation indoors)(Exfiltration of indoor air)- (Indoor
absorption of pollutants)}
and this reads as

V.dCin/dt = V.ACout + S VACin VD Cin
where
V = Volume of structure (volume unit)
A = Ventilation rate (time1)
S = Rate of indoor pollutant emission (mass/time)
D = Decay rate within structure (time1)
54
Cin = Indoor pollutant concentration (mass/volume)

Cout = Outdoor pollutant concentration (mass/volume).
Since the air volume inside the compartments is
constant when the submarine dives underwater, the infiltration
of outdoor air is zero. In the same manner, the exfiltration of
indoor air does not take place and therefore this factor is
neglected. Therefore, the Mass-Balance equation is reduced to
Accumulation rate ( V.dCin/dt) = S VDCin
In cases where no elimination process is adapted for
the pollutant for certain time, the Mass-Balance equation further
reduces to
V.dCin/dt = S
It is very clear from the Mass-Balance equation that the
factors S and D are very important. It is possible to get a clear
idea of the indoor air quality, if we know these parameters for the
submarine compartments.
A corollary of this Mass-Balance equation is the multizone model equation more than one compartment air quality has
to be modelled. But in a submarine, since central ventilation
takes place, the entire indoor space can be considered as one
zone only.
7.2
CASE STUDY
A typical submarine manned by 30 persons has an
indoor volume of 600 m3. Air circulation in two compartments is
centrally controlled and the air movement is 50 m3/hr. The
ambient temperature is 20oC and pressure is 1.1 bar. A model for
carbon dioxide in the indoor environment of submarine has to be
developed.
At the start, atmospheric air has a level of 0.03 per cent
carbon dioxide and hence 600 m3 has a total volume of 300 or
0.3litre of carbon dioxide zero time. A person generates 25 litres of
carbon dioxide per hour; hence 30 men generate 750 litres in one
hour, or 6000 litres in eight hours. When the level of carbon dioxide
in the ship reaches 1.0 per cent during continuous underwater
diving, say approximately in eight hours, the carbon dioxide
content in the 600 m3 space is 6000 litres. From this point onwards,
the 30 men produce 750 litres of carbon dioxide every hour. This
figure represents S in the Mass-Balance equation, applying a
Air Pollution Modelling in Submarines
single zone Mass-Balance equation

dCin/dt = S = 750 l
The problem is now to eliminate this 750 litres as and
when formed so that the cabin level of carbon dioxide is static at
1percent. For absorbing the liberated carbon dioxide,
absorbents such as sodalime or molecular sieves in sufficient
quantity are to be used in canisters. By modelling the carbon
dioxide generation, it is possible to manage the indoor
environment of submarine continuously during cruises1.
REFERENCE
1.
Nagda, N.L.; Rector, H.E. & Koontz, M.D. Guidelines for

monitoring indoor air quality. Hemisphere Publishing
Corporation, USA, 1987, pp. 12-18.
55
CHAPTER 8
MONITORING AIR QUALITY IN SUBMARINES
Air quality monitoring in submarine is mandatory to know
the level of individual pollutant, to calibrate the life-supporting
equipment and to start anti-pollution controls in the vessel. When
a pollutant reaches an alarming level, it should not only be
detected, but also brought under control. The techniques of
monitoring air quality indoors are not very different from that of
ambient air monitoring, but only with some modifications to suit
the specific work environment. The methods employed for the
submarines are similar to the ones adopted in a spacecraft. Here
again, the methods are to be applied accurately, rapidly and costeffectively to achieve the benefits. The instrumentation and
devices developed for monitoring the submarine environment
thus adopt the low-cost, often once-through, rapid and accuracyoriented features.
The selection of sites for monitoring indoor air pollutants
has to be chosen judiciously on the basis of men present at
pollutant-generating zones. As seen from the layout of a submarine
(Chapter2), the pollutants are generated in engine room, aft
compartment and battery pits. When the ship dives underwater,
the engine rooms ventilation is cut off from the main stream and
this volume of the space is not considered. The battery rooms are to
be monitored for the suspect gases, e.g. hydrogen, sulphuric acid
aerosol and stibine specifically, as these gases occupy the bottom
portions of the compartment. Therefore, the battery pit is another
site for sampling the air pollutants. The remaining preferred site
is the living space, where many men are engaged in work. They
produce many metabolic products which are pollutants. Sometimes
when the vessel snorts, the engine room also partially experiences
contamination with diesel exhaust gases and these spaces are to
be monitored.
8.1
SAMPLING TECHNIQUES
Essentially four types of sampling techniques are
adopted for air monitoring indoors1. These are:
58
Grab sampling: A technique known for collecting specific

quantity of air in plastic bag or vacuum-created glass flask or
stainless steel pressure bottle.
(b) Integrated sampling: Facilitates absorption of air pollutants in
liquid gas washers or bubblers.
(c) Continuous monitoring: Allows sampling and simultaneous
measurement of real-time concentration using physical
instruments, such as colorimeters, conductivity cells or pH
monitors.
(d) Personal monitors: In the form of tapes or impingers with or
without a small battery operated pump2 or passive samplers,
which work on the driving force of diffusivity of gases and
vapours or chemical detector tubes.
A combination of the above-mentioned sampling
techniques is employed for air quality monitoring in submarine 1.
The detailed discussion on the methods follows in the coming
pages.
(a)
8.2
ANALYTICAL METHODS
The most commonly practised analytical methods with
minimum laboratory facilities for indoor air pollutants are
described in this chapter. These are approved by EPA, WHO,
ACGIH and recognised organisations.
8.2.1
Carbon Monoxide
Indoor buildup of this gas in air is mainly due to the
escape from the engine compartment, where the diesel oil burns
for propulsion.
8.2.1.1
Non-dispersive infrared absorption

Non-dispersive infrared (NDIR) spectrometer is used for
accurate determination of carbon monoxide in air 3. The analyser
works on the principle of specific absorption of radiation by the
carbon dioxide molecule kept in a cell. Most equipment designed
for this purpose function on the double beam principle and
operate at atmospheric or slightly above one bar pressure. The
absorption is independent of temperature changes of ambient air
as well as flow variations but sensitive to vibrations.
In the actual NDIR spectrometer, infrared radiation
emitting from two separate sources is directed through reference
and sample cells respectively and are combined in a beam
combiner. Then the radiation enters detector cell which is sensitive
to changes of carbon dioxide concentrations. As a result a signal
is registered in the membrane of the condensor microphone of the
detector and this is further amplified. When the air is passed
Monitoring Air Quality in Submarines
through the sample cell for carbon monoxide concentration

analysis, it absorbs infrared radiation and the amount of radiation
reaching the detector is reduced and hence the detector shows a
reduced signal.
One important prerequisite of NDIR analyser is to adjust
the zero and span by using pure nitrogen and a mixture of known
concentration of carbon monoxide in nitrogen respectively. The
interference due to water vapours in the estimation is not ruled
out; but this can be minimised by : (i) passing air samples through
silica gel, (ii) maintaining constant humidity in the sample as
well as calibration gases, and (iii) by using narrow band optical
filters in combination with the above two techniques. The
interference due to carbon dioxide is minimal at normal
concentrations in air. The analyser is applicable to online or
batch-type collected sample and works in the concentration range
of 0-50 ppm with the least detectable limit of 0.5 ppm.
Method: Zero air, certified to contain less than 0.1 mg/m 3 of
carbon monoxide, and a calibration gas with 40 ppm of carbon
monoxide in nitrogen, are employed. The analyser is calibrated to
zero using zero air. Then the analyser response is adjusted to at
least 80 per cent of the total scale using the calibration gas, and
the reading recorded. The calibration gas is diluted with zero air
and about five sub-calibration gas mixtures are made, and for
each one the reading is noted. With these readings a calibration
graph is drawn. Ambient carbon monoxide concentration in any
sample can now be determined by reading the analyser response
from the calibration graph. A sketch of the NDIR analyser is given
in Fig. 8.1.
SAMPLE IN
SAMPLE CELL
MOTOR
LAMP
TRIMMER
REFERENCE CELL
FILTER
CELL
D'
DETECTOR
TO
MICROPROCESSOR
CHOPPER
Figure 8.1. Line sketch of NDIR instrument

Source: WHO, 1976.
59
60
8.2.1.2
Comowarn
Comowarn instrument can be used for the continuous
monitoring of carbon monoxide in air. It functions on the principle
of electrochemical oxidation of carbon monoxide to carbon dioxide
in a cell4. The electrochemical sensor contains a working
electrode (anode), a counter electrode (cathode) and a reference
electrode in an acid electrolyte. Constant voltage of the cell is
maintained between anode and reference electrode by means of
potentials. At the anode, electrochemical oxidation of carbon
monoxide occurs at specific voltage and accordingly the current
proportional to the carbon monoxide concentration flows through
the sensor.
CO H2O CO2 2H 2e
1
2
O2 + 2H+ + 2e- H2O
This is amplified and the concentration of carbon

monoxide is read directly. Another feature of this sensor is that at
the cathode, electrochemical reduction of atmospheric oxygen
occurs thereby replacing the same quantity of water consumed in
oxidation and thus enhancing the life of sensor.
To avoid the interference of gases, such as nitrogen,
sulphuric oxide, hydrogen sulphide, etc. a carbon filter is provided
at the entrance of the analyser, which removes all these
interfering gases.
8.2.1.3
Detector tube
Detector tubes are widely used for on-the-spot
determination of gaseous pollutants. A line diagram of the
detector tube for carbon monoxide is shown in Fig. 8.2.
Figure 8.2. Chemical detector tube and bellows

Source: Dragerwerke, Lubeck.
Structurally, a detector tube is a glass tube (125 mm

length, 5 mm dia) sealed at both ends and containing a chemical
reagent upto 35 mm length at the centre. On either side of the
reagent bed glass wool plugs or ceramic beads are placed and
both ends sealed. The detector tube is ready for use when
required. Small rubber bellows or syringes are employed to suck
the air from the atmosphere through the tube. The bellows are
so designed that one complete filling takes in 100 ml of air at a
slow rate. Normally, these bellows function for a continuous
operation upto 20 strokes, i.e. to suck 2000 cc of air from ambient
atmosphere.
Method: Both tips of the detector tube are broken at the groove
provided in the bellow and the tube is then connected to the
bellow in the direction indicated by arrow. The air sample from
the atmosphere can now be sucked through the tube at a steady
rate by pressing the bellows and also counting the number of
strokes. As a result, pollutant in air reacts with the chemical
reagent in the detector tube, and a colour band visualised in
length or intensity, is formed. A measure of the length of colour
band or the intensity of colour on entire reagent beds gives a
measure of the pollutant in air.
The reagent bed consists of silica gel and supporting
chemical, which is capable of reacting with carbon monoxide
instantaneously. Several chemicals react with carbon monoxide
on account of its high reactivity. Some features on the nature of
reaction and colour development that takes place in detector
tubes are recorded in literature 57.
The number of strokes of bellow, which permit the
atmospheric air into the tube is determined from the knowledge
of the gas concentration, e.g., if the carbon monoxide concentration
in air is in the range of 5-150 mg/m 3, atleast 10 strokes
(equivalent to 1000 ml) have to be passed into the tube, and if the
ambient carbon monoxide concentration is in the range 100-800
mg/m3, only one or two strokes (i.e. 100 to 200 ml) are sufficient.
Since the flow rate is dependent on particle size, surface area and
porosity of packing of the reagent impregnated silica gel, careful
judgement has to be made while pressing the bellows. The chemical
detector tubes for carbon monoxide are sensitive enough in the
temperature range of 10 to +90 C and normal atmospheric
humidity. They have a reasonable shelf-life of two years.
8.2.1.4
Iodine pentoxide method

This method has been developed at American Gas
Association Laboratories, Cleveland, Ohio 8. The flue gas
containing carbon monoxide is first freed from unsaturated
61
62
hydrocarbons, aldehydes and water vapours by passing through a

chromic acid wash trap and then through potassium hydroxide
bubblers to remove carbon dioxide and acid sprays, and
thereafter through phosphorus pentoxide trap to remove
moisture in the air. Thereafter, the dry air containing carbon
monoxide alone is passed through a U-tube containing iodine
pentoxide, where it reacts to produce free iodine. Iodine is
titrated against sodium thiosulphate and from this value the
concentration of carbon monoxide is calculated. The reactions
are:
5CO I 2O 5 5CO 2 I 2
I 2 2Na 2S 2O 3 2NaI Na 2S 4O 6
From stoichiometric considerations,
140 g of CO = 253.8 g of I2 = 496.4 g of Na 2S 2O 3 .5H 2O
8.2.2
Carbon Dioxide
The buildup of carbon dioxide in the ship takes place in
interior compartments, subways, corridors, tunnels and near
incinerators or welding units. Carbon dioxide is determined by the
following methods:
Titrimetric method8
Electrochemical measurement 9
Refractive index method
Chemical detector tube4, 10
In addition, sophisticated methods based on photoacoustic
spectrometry,
infrared
spectrometry
and
gas
chromatography, mass spectrometer, Raman spectra, etc. are also
reported in the literature 11-13. However, these are not described
here.
8.2.2.1
Titrimetric method
A known volume of air to be analysed for carbon
dioxide is passed through a bubbler containing known quantity
of barium hydroxide solution together with barium chloride.
Depending upon the concentration of carbon dioxide in air, and
also length of sampling, either 0.10 N or 0.01 N Ba(OH)2 solution
is used. The presence of barium chloride aids in retarding the
hydrolysis of barium carbonate that forms in the bubbler. After
sampling, the contents are transferred into a titration flask, air
swept with nitrogen and the excess barium hydroxide titrated
against 0.05N oxalic acid using phenolphthalein or
thymolphthalein indicator. One ml of 0.0454 N oxalic acid is
equivalent to one mg of carbon dioxide in the air.
CO 2 Ba (OH )2 BaCO 3 H 2O
8.2.2.2
Electrochemical measurement
An electrochemical analyser based on an electrolytic cell
(with gel electrode) is the on-the-spot measuring equipment for
carbon dioxide. The principle of the method is to isolate carbon
dioxide from other gases by diffusion through a membrane (which
is capable of allowing only carbon dioxide to pass through)
followed by registering the pH developed in the cell. The electrode
potential between the pH and reference electrodes is proportional
to the logarithm of carbon dioxide in the air.
The sensor is very reliable and operates at temperatures
between 0-55 C and pressures between 0.5-1.5 bar and has a
shelf-life of 12 months.
8.2.2.3

The generally accepted differential refractometric
method wherein the refractive index of air sample containing
carbon dioxide inflow is compared to that of air and the
difference in refractive index correlated with the concentration of
gas has found application in the continuous measurement of
carbon dioxide. A typical sketch of the refractive index
measuring instrument is drawn in Fig. 8.3.
HEXAGONAL PRISM
MIRROR
LAMP
PE TUBE &
MICROPROCESSOR
LENS
REFERENCE
(AIR)
SAMPLE
TWIN FLUID PRISM

ASSEMBLY
Figure 8.3. Sketch of refractive index measurement for CO2
Source: Ewing, G.W., 1975.
The angular displacement of light beam on passing

through two fluid prisms results in a difference in refractive index,
63
64
which can be followed even upto ppm levels in the refractive index
value. Pure compartment air exposed over anhydrous calcium
chloride passes through the reference limb and dry air with carbon
dioxide passed through sample cell and the difference in refractive
index for yellow (sodium D-line) is registered. From this reading, the
concentration of carbon dioxide in air is directly read on the
calibrated scale of instrument. The range of carbon dioxide
calibration scale is 04 per cent of dry air.
8.2.2.4
Chemical detector tube method

Chemical detector tubes for carbon dioxide are
prepared from any of the reagents systems shown below:
Hydrazine crystral violet
Diethylene triamine and crystal violet
Triethylene tetramine and crystal violet on silica gel

support.
When compartment air is sucked through the detector
tube during 10 strokes (i.e. 1000 ml), a blue colour band develops
on the reagent and the length of the colour reads for the
concentration of carbon dioxide.
8.2.3
Hydrogen
Hydrogen in air is determined by measurement of
thermal conductivity in the sensor.
8.2.3.1
Thermal conductivity analyser

A wheatstone bridge with four arms is constructed. Of
these, two oppositely placed temperature responsive resistances are
connected for noting response on measuring gas. In a similar
manner, other two equal chambers are interconnected (Fig. 8.4).
Finally, the Wheatstone bridge circuit resistances are connected
Figure 8.4. Line sketch of TCD hydrogen analyser

Source: Instrumentation Ltd, Kota, 1977.
to a constant voltage source for providing temperature, which

depends on the thermal conductivity of reference gas as well as
the gases being measured. The reference gas is kept in one set of
two opposite resistances array either sealed or constantly
flowing. From the other set, the gas to be measured is passed.
On applying constant voltage to all the resistance sets,
depending on the type of gas and its concentration, an imbalance
is created in the voltage, which is proportional to the component
gas (namely, hydrogen) being measured. The unbalanced voltage
is amplified and a DC signal proportional to the concentration is
shown on meter, and alternatively an alarm set into operation by
a microprocessor14. A sketch of the TCD hydrogen analyser is
shown in Fig. 8.4.
8.2.3.2
Mass spectrometric method

Hydrogen present in air is best determined by a mass
spectrometric method. Practical details of this sophisticated
technique are described in detail in Appendix C.
8.2.4
Oxygen
Oxygen is a life-supporting constituent of air in
submarines and has to be maintained at a level of 201 per cent
(V/V). It is, therefore, necessary to measure the level of oxygen
continuously during the cruises. Oxygen in air is determined in a
number of ways.
8.2.4.1
Volumetric method
A known volume of air containing oxygen is held in a
gas pipette and the reading on pipette scale noted. This air is
brought in contact with potassium pyrogallate to allow the oxygen
to react with the pyrogallate. As a result, the reading on gas
pipette changes; the difference between initial and final readings
indicates the volume of oxygen present in the entrapped air of
gas pipette. The method is cheap, simple and accurate15.
8.2.4.2
Paramagnetic oxygen analyser

Molecular oxygen behaves paramagnetic, which is a
unique property possessed by this permanent gas. This property
is derived from its non-compensatory angular momentum of
electrons in the atomic structure and is called magnetic dipole
moment. These dipoles are oriented in the direction of the field
under the influence of an external magnetic field. However, if the
temperature is raised this orientation of dipoles decreases. In the
design of instrumentation for oxygen these principles are
translated into sensing devices16. A line-sketch of a paramagnetic
oxygen analyser is shown in Fig. 8.5.
65
66
TRANSVERSE TUBE
FOR OXYGEN FLOW
(LEFT RIGHT)
MAGNET
O2
Figure 8.5. Paramagnetic oxygen analyser

Source: Instrumentation Ltd, Kota, India, 1977.
The instrument has a ring chamber made up of hollow

ring arranged in a vertical plane with a gas inlet at the bottom
and an outlet in the top portion. The two halves of the ring
chamber are connected by a thin-walled glass tube. This
transverse tube has taped wire winding on its outside for heating
purposes. The winding coil is part of a wheatstone bridge circuit
whose one half is located in the field of a permanent magnet. The
measuring gas/air is passed from bottom of a hollow ring to top. If
there is no oxygen in the sample, there will not be any flow in the
transverse tube. If the sample has oxygen, it is first attracted by
magnetic field into the transverse tube. In case, the gas flow is
heated in the magnetic chamber, there will be decrease in
magnetic susceptibility of paramagnetic oxygen molecule and
thus the heated gas is driven away by the cold gas entering from
left hand side (shown by arrows). Thus, a gas flow arises inside the
transverse tube from left to right and this flow is denoted as
magnetic wind, its velocity is dependent on oxygen concentration
in the sample. The magnetic wind in turn cools down the left side of
the winding tape more than the right side thereby causing a drift
in Wheatstone bridge balance. The voltage difference of the bridge
is thus proportional to the concentration of oxygen in the sample.
Paramagnetic oxygen analysers are very sensitive and
accurate in the ranges 0-21 per cent. They are very robust in
construction and hence tolerate pitching, rolling and vibrations.
8.2.4.3
Electrochemical analyser
The analyser comprises a polarographic sensor for
oxygen. The sensor is constructed from a gold cathode and silver
anode, both immersed in a gel electrolyte. The opening of the
sensor is sealed by a teflon membrane, which permits only oxygen.
Now, a small potential is applied between the electrodes. Oxygen
diffusing through the teflon membrane penetrates into the
electrolyte and gets reduced electrochemically at the cathode,
thus producing small current. This signal is amplified and
calibrated directly against the oxygen concentration (or partial
pressure) in air. The sensor is insensitive to other gases, very
rugged and not affected by even cent per cent humidity. It can
withstand an atmospheric pressure of two bar. It suits the
submarine environment16, 17.
8.2.5
Hydrocarbons
Two types of hydrocarbons aliphatic and aromatic are
present inside submarine compartments. In the engine room these
are noticed on more than one occasion, whereas in the wardroom or
aft compartment the concentrations are too low to be noticed. These
are determined according to the following methods:
8.2.5.1
Chemical detector tube

All aliphatic hydrocarbons respond to reaction over a
chemical detector tube4. The reagent impregnated on silica gel is
potassium dichromite and selenium dioxide. Aliphatic organic
compounds present in air produce an orange colour and aromatic
compounds deep red colour. From the length of coloured band,
the concentration of the hydrocarbon is deduced.
8.2.5.2
Methanometer
A compact Wheatstone bridge with two pairs of pelletised
filaments constitute a methanometer. The hydrocarbon (methane
series) enters the chamber where a pair of filaments (active type
which heat and burn the gas) are fixed and burn thereby producing
an electrical imbalance in the circuit. A measure of this heat
indicates the concentration of hydrocarbon. The methanometer is
a portable equipment manufactured by Mine Safety Appliances
Ltd (MSA), Kolkata, India. The Warnex, manufactured by
Dragerwerk, Germany, also operates on a similar principle18,4.
8.2.5.3
NDIR
All aliphatic hydrocarbons can be determined by NDIR

method (with propane standard) according to the method already
described under carbon dioxide (para 8.2.1.1).
67
68
8.2.5.4
Gas chromatographic techniques

Gas analysis employing a gas chromatograph (GC) with
silica gel column can be effected. In some cases, preconcentration of sample can be achieved first by adsorbing the
gas at subzero temperatures over silica gel followed by GC
separation and characterisation using suitable detectors. All
aliphatic and aromatic hydrocarbons can be estimated following
this technique19, 20.
8.2.5.5
GC-MS technique
A GC coupled with a mass spectrometer (MS) will serve

as an excellent device for characterising both aliphatic and aromatic
compounds present in air. The method does not require standards
of the individual compounds as the m/e gives the mass values
from which the most probable compound is characterised. The
m/e values are typical indices for organic species. Although these
are ion masses, a close examination of the m/e values reveals the
total structure/feature of the organic compound. A single m/e value
sometimes may indicate the possibility of several compounds, for
example, the value 15 may denote ammonia or water; but from
the other data obtained, a decision on the compound can be taken.
A computerised data bank for m/e values is currently available.
8.2.5.6
Photoacoustic spectrometry
A photoacoustic spectrometer (PS) consists of an IR light
source, emitting radiation, which passes through chopper and filter
and then enters a chamber filled with molecules. The modulated
IR light is absorbed by molecules, whose internal temperature and
pressure thereby goes up resulting in a sound wave. The sound is
sensed by a microphone and the signal processed to estimate the
concentration of gas in air sample. The method is very sensitive
and accurate. This sophisticated PS is manufactured by Bruel &
Kjaer, Denmark
8.2.6

Incomplete combustion of wood, coal, oil and other
organic wastes produce a variety of organic compounds of which
polynuclear aromatic hydrocarbons are the notorious toxins.
These are shown in Table 3.2 (Chapter 3). The following
concentrations of these hydrocarbons are recorded in some of the
processes, for e.g. B(alpha) pyrene/1000 m3 ~ 6 x 106 g (20 cm
away from coal tar pitch kettle) :
*
*
*
*
~ 3 105 g (in undiluted cigarette smoke)

~ 2.9 105 g (in African hut during cooking) and
2.0 104 g in London city air (highest recorded)
1 10-2 g in a rural area in pacific coast.
8.2.6.1
Collection of polynuclear aromatic hydrocarbons

from air
Some of the hurdles in the sampling are photooxidation, incomplete collection and loss during analytical
procedures. The photo-oxidation can be minimised by taking
precaution to shield the sampling filter from direct daylight and
storage of sample in dark and under refrigeration. The normal
filtration of large volume of air under velocity can also be
regulated. The third factor for loss is in analysis, and this occurs
in extraction procedures from soot and in chromatography. This
can be overcome by using an internal standard (not a compound
present in mixture) or a 14C labelled compound and applying
suitable correction.
Method: The polynuclear aromatic hydrocarbons (four or more
ring components) are quantitatively collected by filtration. The
filter paper is extracted with benzene, and the extract
chromatographed on alumina. The eluted and fluorescent column
fractions are subjected to the following quantitative estimations:
(a)
Benzo (e) pyrene fraction is dissolved in sulphuric acid and
the fluorescence measured at 362 nm.
(b)
Benzo (d) pyrene is similarly taken in sulphuric acid and
determined by fluorescence at 520 nm.
(c)
Perylene is dissolved in pentane and the fluorescence
measured at 430 nm, whereas benzo (k) fluoranthene is
quantitatively estimated at 401 nm. Following similar
methodology, Sawicki (1957) concluded that the presence of
polynuclear aromatic hydrocarbons in air samples to be of
the ratio 8:5:3:1 for BP, BeP, BkF and perylene,
respectively. However, this ratio is dependent on traffic
conditions and hence is approximate.
8.2.6.2
Detection of polynuclear aromatic hydrocarbons

Piperonal chloride reacts with polynuclear aromatic
hydrocarbons in presence of trifluoroacetic acid to produce colours,
such as blue, blue-green or light purple, which can be
characterised for specific type of compound at a specific
wavelength in visible spectrum. The following procedure is
adopted:
Preparation of reagent: Equimolecular amounts of piperonal
and phosphorus pentachloride are mixed in a flask maintaining
the temperature below 40C. Thereafter, the product is warmed to
45C for 2-4 minutes, cooled and added to excess of ice water when
a solid mass is obtained. It is crystallised from pentane
immediately and stored.
69
70
The extract of suspended particulates containing the

polynuclear aromatic hydrocarbons in chloroform (a few drops) is
kept in a small test tube and then 5 ml of trifluoroacetic acid
followed by a few crystals of piperonal chloride are added and
shaken thoroughly. The homogeneous mixture is allowed to
remain for some time, and the colour developed is observed
visually and measured using a colorimeter. Table 8.1 shows the
colours displayed by some of the polynuclear aromatic
hydrocarbons on reaction with piperonal chloride.
Table 8.1. PAHpiperonal chloride colour development
Compound
Colour
Absorption max.
(nm)
Benzo-alpha-pyrene
Yellow-brown
Anthracene
Yellow-green
732
Fluoranthene
Blue
640
2,3-Benzofluorene
Green
645
Chrysine
Green
730
Fluorene
Purple
580
9-9' Bifluorenyl
Purple
587
1-Phynylnapathalene
Blue
627
1-1' Binaphthyl
Light
Pyre ne
Green
green
753,563
620
680
Source: Jacobs MB, (1960).
8.2.7
Freons
The determination of freons in the compartment air is
made as follows:
8.2.7.1
GC-MS technique
Air containing the freon substances is pre-concentrated
and separated into individual species on a gas chromatograph.
These individual species are ionised in a mass spectrometer and
from a plot of m/e values, the individual freons are determined
(Appendix C).
8.2.7.2
Freon meter
Freon compounds are thermally cleaved into several
chloro-organics and are estimated using a freon meter. The freon
meter consists of a Wheatstone bridge circuit and measures the
imbalance of current voltage caused on one pair of resistances,
which come into contact with the cleavage products of freon. Freon
compounds are thermaly cleaved into several chloro-organics and
are estimated using a freon meter.
8.2.7.3
Detector tube
This device has been recently developed at Dragerwerk,
Lubeck, for measuring CFCs. The tube consists of two separate
small tubes connected one after the other through a shrinkage
hose pipe. These are notified as Tube 1 (pyrolyser) and Tube 2
(detector). Tube 1 consists of mere pyrophoric iron, wherein
thermolysis of freons first occurs instantaneously. Tube 2 consists
of the reagent for measurement of hydrogen chloride (through pH
measurement).
To start with, the two tips of Tube 1 and Tube 2 are broken
to allow free passage of air throughout the length. The oxygen in
the atmosphere is sufficient to react with pyrophoric iron laid in
tube (upto 5 mm length) and it glows into bright yellow. The heat
generated in this process is sufficient to cleave the freons into
hydrogen chloride. As further air sample is sucked into Tube 1,
the freon breaks down to hydrogen chloride, which is subsequently
reacted in Tube 2 to offer a measurement of freon.
The freon detector tube is not quite selective for a single
freon gas. For this reason, a millimeter scale to show the measurement
of hydrogen chloride generated by different types of freons, e.g. 1,1,2
trichlorofluoroethene (RH3), 1,2dichlorofluoroethene (RH4),
bromotrifluoroethene (R13) and trichlorofluromethene (R11), etc.
which was calibrated against these compounds has been provided
on the tube. The measuring range of the tubes is 100-3000 ppm
(the TLV levels for most of the CFC's is around 1000ppm).
The tube does not become hot externally as the
shrinkage hose pipe covers the outside portion where heated
pyrophoric iron is positioned.
8.2.7.4
IR and PAS techniques

All freons absorb infrared radiation and hence are
estimated either by direct measurement (MIRAN) or by
photoacoustic spectrometry (PS) (Appendix B).
8.2.8
Organics
The analytical methods of estimation of individual
organic compounds differ for each category and some typical
methods for estimating the individual compounds, namely, MEA,
acrolein, formaldehyde, etc. are recorded.
8.2.8.1
Acrolein
When foodstuffs containing vegetable oil or fat are fried
over a pan at high temperatures, the vapours of acrolein
CH2=CHCHO, a stuffy compound are formed.
71
72
Sampling: The sample is absorbed in either water or preferably in

5 per cent aqueous alcohol solution kept in a bubbler by passing
air at the rate of 20-30 l/hr for a few hours duration depending on
its concentration.
Rippers method: This is based on addition reaction of acrolein
(any aldehyde) with alkaline potassium bisulphite solution.
RCHO KHSO 3 RCH (OH ).SO 3 K

The excess bisulphite is estimated iodimetrically.
This estimation is a general one and is applied to
formaldehyde and acetaldehyde as well. For conclusively
establishing the quantity of acrolein, permanganate estimation
has to be performed.
Permanganate estimation: A known volume of the test sample
solution is transferred to a 200 ml glass stoppered conical flask
and made strongly acidic with sulphuric acid. A known volume of
potassium permanganate solution is added and the mixture
heated for 15 min to oxidise the acrole (including the cleavage of
double bond). After this, a known volume of standard oxalic acid
is added (in excess) and the excess oxalic acid is estimated with
permanganate solution (A blank is simultaneously run). From the
quantity of potassium permanganate consumed for oxidation
initially, the amount of acrolein is estimated 8.
8.2.8.2
Formaldehyde
Formaldehyde is a constituent found in air indoors of
offices, kitchens and submarines where panelling of surfaces is
made with resins. It is determined as follows 21:
Sampling: Indoor sampling is carried out over 24 hrs (outdoor
over 250-280 min) in bubblers containing 50 ml of distilled water.
The samples can be stored in refrigerator.
Estimation: A colorimetric method (Schryvers reaction) in which
an intense magenta colour is formed on reaction of formaldehyde
hydrazone solution with potassium ferricyanide solution in the
presence of an excess of hydrochloric acid, has been followed.
The minimum detectable limit of HCHO is about 0.5 g in the
measurement and the intensity of colour is proportional to the
concentration of formaldehyde.
Passive sampling device: Measurements were made for oneweek period using these devices in main living area, kitchen,
and bedroom of the homes. Lawrence Berkeley Laboratories (LBL)
developed these devices. These consist of glass vial containing a
glass fibre filter treated with sodium bisulphite and a removable
cap. The sensitivity remains at 12 g/m3 over a one week period,

with an accuracy of 15 per cent. The samples are to be prepared
in oxygen-free atmosphere (to avoid oxidation of bisulphite) and
dried under vacuum. The samplers were stacked on stand, or
hung near the usual breathing height in each room, sitting height
in bathrooms, etc. and always placed away from walls, stoves and
sinks. After one week sampling, they were capped and analysed in
the laboratory adopting chromotropic acid method.
Detector tube: A detector tube (0.5-10 ppm range) employing the
reagents xylol and sulphuric acid (embedded over silica gel) have
been most widely employed for estimating the formaldehyde, and a
rose colour compound is formed as the end product of reaction4.
HCHO C 6 H 4 ( CH 3 ) 2 ( CH 3 ) 2 C 6 H 3 CH 2 C 6 H 3 ( CH 3 ) 2
(Formylation-A)
A H 2SO 4 Addition product (Rose colour)
Interferences:
Acetaldehyde Green colour
Acrolein
Brown colour
8.2.8.3
Monoethanolamine
The estimation of monoethanolamine in submarines
where these scrubbers are installed is mandatory. Monoethanolamine is determined rapidly by the following
techniques22,11,12:
Detector tube: The chemical reagent employed in the detector
tube for estimation of monoethanolamine is copper sulphate. This
chemical is impregnated on wet filter paper pulp (support) in the
centre of the detector tube. When exposed to menoethanolamine
in air, the colour of the reagent changes to blue and the length of
the band gives a measure of the amine present.
GC-MS technique: Compartment air, when subjected to gas
chromatography mass spectrometric analysis offers the
identification and estimation of monoethanolamine (Appendix C).
8.2.9
Chlorine
Chlorine reacts with O-toluidine and produces a yellow
colour. The intensity of the colour is compared with the colour of
permanent standards made out from potassium dichromate
(permanent standards) and thereby the concentration of chlorine
in air is measured8.
8.2.9.1 Colorimetric Method
Reagents:
(a) O-Toluidine solution: 1g of O-toluidine is weighed and ground
in a mortar with 5 ml of dilute hydrochloric acid (1:4). The clear
solution thus obtained is transferred into an 1 l reagent flask and
73
74
diluted with similar acid. The reagent is stored in amber-coloured

bottle and can be used upto six months.
(b) Copper sulphate reagent: 1.5 g of copper sulphate CuSO4.5H2O is
dissolved in 1 ml of concentrated sulphuric acid and then made
upo 100 ml.
(c) Potassium dichromate reagent: 2.5 g of potassium dichromate
is dissolved in 1ml concentrated sulphuric acid and made upto
100 ml.
Permanent standards: Ten permanent standards are made out of
mixing reagents (b) and (c) as shown in Table 8.2. The colour
comparisons are made in Nessler's tubes100 ml capacity with a
mark at 300 mm from bottom-by filling the tubes with solutions
upto 240 mm mark level. These permanent standard tubes are
protected from dust and light by sealing with a microcover.
Estimation: An acquit of chlorine sample is taken in a Nessler
tube and 1 ml of O-toluidine reagent added to produce yellow colour.
This is kept aside in dark for 5 min (not beyond 15 min). After full
colour development is achieved, the sample is compared with the
permanent standards under a daylight lamp or against a white
background with lamp and the concentration of chlorine read from
Table 8.2.
Table 8.2. Permanent chlorine calibration standards
Chlorine
(mg/100 ml)
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Copper sulphate solution

(ml)
8
8
8
8
8
8
8
8
8
Dichromate solution
(ml)
16
22
28
33
38
44
50
57
66
Source: Jacobs MB , (1949).
Alternatively, colorimetric estimation of the sample can

be adopted at a wavelength of 445 nm.
8.2.9.2
Detector tube
Silica gel impregnated
placed in the chemical detector
chlorine is passed through the
band develops on the reagent
with O-toluidine is the reagent

tube 4. When the air containing
detector tube, a yellow colour
bed. The length of this band
indicates the extent of chlorine in the air. The range of chlorine

measurement is between 0-1 per cent.
A chemicasette developed by MDA Scientific Inc,
Illinois, USA can also be employed for detection and estimation of
chlorine in trace quantities.
8.2.10
Halocarbons
The increasing use of refrigerants, degreasing agents,
paint removers, cleaners, polishes and fire extinguishers leave
residues of these compounds in the indoor environment. Most of
the halocarbons and the constituents in these compositions are
toxic and their decomposition products are also toxic. The method
for determination of halocarbons in air is described.
Combustion method: Moist air and the halocarbon are combined
and cleaved at high temperature, say 1000-1100 C over a silica
tube. An alternate procedure is to heat the same mixture over hot
platinum foil at 850C. In both cases, the resulting hydrogen
chloride is trapped into a bubbler containing 5 per cent aqueous
potassium hydroxide. From these traps, the quantity of chlorine
generated after cleaving the pollutant is calculated. In the
combustion experiment, moist air assists in generating hydrogen
chloride instead of chlorine gas or chlorocarbons. Also, regulation
of air flow to a slow rate of 2.5ltr/min helps in greater conversion
to hydrogen chloride8.
8.2.11
Nitrogen Dioxide
The mixture of oxides of nitrogen (NOx) namely, nitric
oxide and nitrogen dioxide can be converted fully to nitrogen
dioxide by oxidation and this gas determined following several
techniques24. These include:
8.2.11.1 Saltzman method
The nitrogen dioxide in the ambient air is converted to
nitrite ion upon contact with an absorbing solution containing
the diazotizing-coupling reagents. The nitrite ion thus formed
reacts with the reagent producing a stable pink colour within 15
minutes and the intensity of colour gives a measure of the
concentration of nitrogen dioxide in air.
The method is calibrated with known concentration of
nitrogen dioxide and diazotizing-coupling reagent. For this
purpose, sodium nitrate is used as standard. NaNO3 (0.74 mole)
produces the same colour as 1 mole of nitrogen dioxide gas.
N-(1-Naphthyl)-ethylenediamine dihydrochloride is the
diazotizing amine and sulphanilic acid is the coupling compound.
The absorbance of the azodye is measured at 550 nm with distilled
75
76
water as the reference. The method is very reliable and NO2 gas
from very low level upto 5 ppm can easily be estimated.
8.2.11.2 Detector tube
The sensitivity of detection of nitrogen dioxide in indoor
environment using detector tube is 0.3 ppm (564 g/m3). The
detector tube comprises a reagent of N-(1-Naphthyl)-ethylenediamine dihydrochloride and sulphanilic acid impregnated over
silica gel and placed in a glass tube. From the length of the pink
stain developed for 10 strokes of inlet air (or 1000 ml), the
concentration of nitrogen dioxide can be read directly.
8.2.11.3 Chemilluminescence method
The chemilluminescence reaction between nitric oxide
and ozone at reduced or atmospheric pressure offers a method of
estimation of nitrogen dioxide in air. The nitrogen dioxide present
in air is first converted to nitric oxide and the total nitric oxide
present in air is recorded. Then the nitric oxide alone present in
air is separately measured; the difference in these values give the
quantity of nitrogen dioxide. The detectable limit of nitric oxide on
instrument is 0.005ppm and the method works in the range
0.005-10 ppm.
8.2.12
Hydrogen Chloride
The acid mist of hydrogen chloride is very toxic to

human beings (MAC 5 ppm ACGIH) and also corrosive for
machinery parts.
Sampling: The acid is trapped in solutions placed in an impinger or
gas washing bubbler. A solution of glycol-potassium carbonatewater in the ratio of 1:1:1 is most convenient. The excess sodium
carbonate is titrated back using standard sulphuric acid thereby
offering an estimation of the acid mist. Further, the chloride content
in the solution is determined by any of the following methods:
8.2.12.1
Fajans method
Very dilute solutions of chlorides can be estimated by
this method. The principle involved is the absorption of dye, e.g.
dichlorofluoroscein (indicator solution) at end point of titration.
Indicator solution: A 0.1 per cent solution of sodium salt of dye
in water is made (about 2.5 ml of 0.1 N NaOH (aqueous) is
required to neutralise 100 mg of the indicator).
Procedure: About 2 to 4 drops of indicator solution is added to
50 ml of the test solution. As the titration is commenced with
silver nitrate, near the end point the solution turns brown and at
the end point it turns sharply to orange. A slight excess of silver

nitrate produces a red colour. From the quantity of silver nitrate
consumed, the chloride content in test solution is estimated.
8.2.12.2 Volhard method
In this method, the chloride, which is trapped in
impinger is reacted with excess silver nitrate to convert it fully into
silver chloride, which is suitably held up at the interface between
aqueous and an invisible nitrobenzene layers. The excess silver
nitrate is titrated (using ferric alum as indicator) with potassium
thiocyanate till the end point (pink colour) is produced8.
Ion selective electrodes specific for estimation of chloride
ion can be used to measure hydrogen chloride (MDA 1991).
8.2.13
Hydrazine
Hydrazine and its salts are very toxic and these are
estimated by wet chemical methods8 described below:
8.2.13.1 Oxidation with iodine
The vapours of hydrazine or its hydrate are trapped in
water and titrated with 0.01N I2/potassium iodide solution in
presence of NaHCO3 to give nitrogen and hydriodic acid. Either
nitrogen or hydrogen iodide can be directly estimated further.
N 2H 4 2I 2 N 2 4HI
This method is most suitable for hydrazine or its hydrate.
8.2.13.2 Oxidation with KMnO 4
Hydrazine salts are titrated against standard potassium
permanganate in sulphuric acid to afford nitrogen gas, which is
measured.
N 2H 4 2(O ) N 2 2H 2O
8.2.13.3 Detector tube
The chemical detector tube for hydrazine was based
on the reaction:
N 2H 4 H
Bromophenol blue
{N 2H 4 }HX
Thus the silica gel column in the detector tube is

containing acidified bromophenol blue, which turns colourless
when exposed to hydrazine vapours. The tubes are made exactly
as described for carbon dioxide4.
77
78
8.2.14
Ammonia
The toxic gas, ammonia, which surrounds the sanitary
blocks as well as industrial areas can be estimated by several
methods. Most popular and simple methods are described below8.
8.2.14.1
Titration method
A known volume of air is passed through two bubblers
in series containing standard 0.02N H2SO4. On completion of
sampling, the contents of the two bubblers are mixed up (with
rinsings) and the excess acid titrated with 0.02 N NaOH solution
using methyl red indicator (1 ml of 0.02N H2SO4=0.00034 g of
ammonia). This method can be applied in field areas also.
8.2.14.2 Nesslers method
Follin-Nesslers reagent, an alkaline solution of double
iodide of potassium and mercury (HgI.2KI) is prepared first. In a
250 ml flask, 30 g of KI and 22.5 g of I2 are treated with 20 ml of
water to make a clear solution. Approximately, 30 g of metallic
mercury is now added and shaken vigorously until the dissolved
iodine practically disappeared (15 min and solution turns hot).
Shaking and cooling of the flask is continued until the red iodine
colour diminishes and green colour of double salt persists. The
absence of iodine in the solution should be ensured by starch test;
thereafter, the solution is decanted, and the mercury is washed
with water, the filtrate made up to 200 ml.
The final Nessler's reagent is made from the above
solution by mixing it with exactly 975 ml of 10 per cent aqueous
NaOH (accurate). The alkalinity of Nesslers reagent is very
important and should be checked by titration with 1N HCl (20 ml
of 1 N HCl should require 11 to 11.5 ml of Nesslers reagent).
Procedure: Ammonia present in air is trapped in 0.02N H2SO4
bubblers. The contents of bubblers are transferred to volumetric
flask after the absorption of ammonia is complete, and made upto
a definite volume. Out of this, 1-5 ml of solution is taken in 150 ml
volumetric flask and 6 ml of Nesslers reagent added and made
up to volume. Simultaneously, a standard (containing 0.4716 g/l,
10 ml of it diluted to 100 ml) is prepared and treated with the same
quantity of Nesslers reagent in a similar manner and compared
with the sample. From this, a relative estimation of ammonia is
made. Even very low concentrations of ammonia can be measured
accurately.
8.2.14.3
Detector tube method

In the detector tube, the support for the chemical
reagent copper sulphate is filter paper pulp made out of
Whatman No. 1, wherein 1.0 g of CuSO4 is added to 10 g of

Whatman No. 1 filter pulp in 200 ml distilled water. After
impregnation, the paper pulp is separated and water removed by
placing in an oven maintained at 80C for 6 hrs. The pale blue
pulp, which is still moist, is cooled to 30C and used as indicating
medium in the detector tube on reaction with ammonia; the
intensity of colour is a measure of this gas22.
8.2.14.4
Ion selective electrode method

Electrodes specific for ammonium and sulphate ions are
developed to measure these contaminants in submarine
environment 2.
8.2.15
Stibine
Stibine (SbH3) present in air is estimated by a
colorimetric method employing Rhodamine B. The gas is trapped
in mercuric chloride solution, trivalent antimony is oxidised by
ceric sulphate in acid medium to quinquevalent antimony,
excess
ceric
sulphate
removed
using
hydroxylamine
hydrochloride and the aqueous portion reacted with Rhodamine
B and the colour measured at 565 nm.
8.2.15.1
Rhodamine method
A solution of 60 g of mercuric chloride in 6 N HCl was

prepared and made upto 1 litre with the same acid; 20 ml of this
solution is taken in a bubbler/impinger and the air containing
stibine is passed through this to trap stibine. Thereafter, the
absorbed solution is transferred to glass stoppered measuring
cylinder (50 ml capacity). The bubbler rinsings are also added and
the volume now stands at 30 ml marking. Out of this sample, 15ml
is drawn into a conical flask, and 0.5 ml of 0.1 N ceric sulphate
solution (prepared from 33 g anhydrous ceric sulphate Ce(HSO4)2,
in 3 per cent sulphuric acid and making upto 1:l. The mixture is
allowed to remain for 1 min during which conversion of Sb 3+ >
Sb5+ is complete. At the end, dry air is blown through the solution
to remove any free chlorine gas generated. Excess ceric sulphate
is removed by the addition of 3 drops of 1 per cent hydroxylamine
hydrochloride solution followed by addition of 5 ml of 6 N HCl. After
this, 1 ml of 0.2 per cent rhodamine solution (filter the
reagent before use) is added and the whole mixture is
transferred into a separatory funnel, and 25 ml benzene added.
79
80
The aqueous layer together with a little benzene is drawn

out after thorough extraction. The organic layer is centrifuged and
8
.
t
8.2.15.2
Methyl fluorone method

The method23 involves the reaction of antimony with
methyl fluorone to produce a strong rose pink colour in solution.
Reagent: 0.1 g of methyl fluorone is dissolved in 100 ml of
industrial spirit and 5 ml of concentrated sulphuric acid and the
solution was diluted one to ten with spirit as required to give a
0.01 per cent solution. This can be used for the estimation of Sb
ions in solution. Absorption solution for the estimation of
antimony is a mixture of these solutions in the order.
(a) 25 ml of 0.2 per cent as Ag2SO4
(b) 2 ml of 0.5 per cent starch solution
(c) 0.5 ml of 0.01 per cent tartaric acid
(d) 0.24 ml of 1N H2SO4
(e) 4 ml of 0.01 per cent methyl fluorone solution.
Standard antimony solution: 0.1067 g of dried anhydrous AR
potassium antimonyl tartrate is dissolved in 1000 ml of water
(1ml of this contains 40 g of Sb). From this stock solution, other
suitable solutions are made.
Complex formation between stibine and methyl fluorone
takes places by passing stibine into 10 ml of absorbent solution in
a bubbler. The colour developed was observed on a photocell and
reading indicated on a meter. The whole reaction occurs in the
absorption cell itself and thereby the concept of a stibine analyser
OUT
IN
FROM PUMP
MICROPROCESSOR
F
REAGENT
Figure 8.5. Stibine meter

Source: Short, D.W.E. & Wheatley, K.H. 1962.
METER
developed as an instrument for shipboard work (Figure 8.5).

Arsine, phosphine and hydrogen have no interference but H2S is
likely to interfere.
8.2.15.3

Silver diethyl dithiocarbamate in presence of pyridine
reacts with stibine and produces a pink stain. The reagent is
embedded on silica gel in the detector tube and the tube was
sealed at both ends. Using this detector tube it is possible to
estimate very low concentrations of stibine (from 0.005-1 ppm)
in air22.
8.2.16

A simple method for trapping the sulphuric acid mist in
air is applied and the resulting acid determined by titration
against sodium hydroxide8.
Device: The glass tube device for holding the filter paper, which
traps the acid has been shown in Fig. 8.6. Two glass tubes each of
Figure 8.6. Collection of H2SO2 aerosol on filter paper
1.5 cm diameter are taken and one end of each tube is expanded
to 3.0 cm by glass blowing. The flared ends are also flattened and
chipped together with the help of screwed jack. Filter paper will be
inserted in the midst of the two flattened ended tubes.
Material: Whatman No. 4 paper is leached with successive
quantities of distilled water to free it from acid and used for
trapping the acid. These papers are dried and cut into size and
stored. A set of two filter discs of a batch whose extract does not
differ more than 0.1 pH is chosen for the test.
Procedure: Two filter discs are placed in the device and air is
filtered at the rate of 50-60 (1400-1700 l/hr). The filtration is
usually done for one hour and where the concentrations have not
built up, it can be prolonged. After this, the paper discs are
macerated in 20ml deionised water and titrated against 0.002 N
81
82
NaOH using a pH meter or an indicator. The quantity of acid present

is calculated as
ppm = (mlbase*N*0.0049*22.41*10^6/98*28.32*Cu ft. air at STP).
8.2.17
Conclusion
From the foregoing account on the submarines, the
following conclusions are drawn:
(a)
The environment in the submarines is very critical and

requires regular monitoring. The analytical equipment and
devices used inside the submarine are required to be accurate,
simple for operation and rugged. These life-support equipment
should not occupy enormous space.
(b) A regular chemical laboratory does not exist on board a
submarine.
(c) Ambient air in the cabins can be collected by means of pumps
and small pressure bottles and sent to shore laboratory at a
convenient time for elaborate analysis.
(d) The personnel on board are trained to operate chemical detector
tubes and certain wall-mounted analysers.
Some of the commercial equipment available for use in
submarines are listed below:
Type of equipment/detector
Principle of operation
Manufacturer
Comowarn for carbon dioxide

Oxycom for oxygen
Electrochemical
Warnex for hydrocarbons
Heat of oxidation
Hydrogen analyser
Thermal
Carbon dioxide analyser
Electrochemical
Beckmann Instruments,
USA; ENDEE Engineers,
Bombay
Stibine Meter
Chemical reaction
Royal Navy, UK
GC-MS
Spectrometer
Finigan-Matt,
Hewlett-Packard
Methanometer for HC
Catalytic reaction
Mine safety applications

Kolkata
Detector tube-CO gas
Chemical reaction
Detector tube for several gases

Personal Protection
Indicators
Gas Sensors
Dragerwork AG, Lubeck
conductivity Perkin-Elmer,
USA
"
"
"
"
"
"
DragerwerkeAG, Lubeck
Americal & Chem. Co.
"
"
Ltd, USA
Semiconductors,
hot wire catalytic,
electro chemical
ENMET Corporation,
USA
REFERENCES
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.
15.
16.
17.
Manual
on indoor air quality. EPRI. Lawrence Berkley
Laboratory, Berkley, California, 1984, pp. 4-3. Final project
report No: EM-3469.
MDA Toxic GAS monitoring systems, Technical Pamphlet,
MDA Scientific Inc. Illinois, USA, 1991.
Selected methods of measuring air pollutants. World Health
Organisation. WHO Offset Publ. 1976, 24, 51.
Detector tube handbook. M/s Dragerwerk A.G. Lubeck,
Germany. 1983. p. 264.
Jacob, M.B. The analytical chemistry of industrial poisons,
hazards and solvents. Interscience Publications, New York,
1949. pp. 402-05.
Silverman, L. & Gardner, G.R. Potassium pallado sulphate
method for carbon monoxide detection. Am. Ind.Hyg.Assoc.J,
1965, 26, 97.
Sephered, M.; Schuman, S. & Kildar, M.V. Determination
of carbon monoxide in air pollution studies. Anal Chem,
1955, 27, 380.
Jacobs, M.B. The chemical analysis of air pollutants.
Interscience Publications, New York, 1960, pp. 93-96, 218.
MINOS atmospher ic oxygen monitor. Beckmann
Instruments Inc, Advanced Technology Operation.
Aratheim, Ca, USA, 1974. Beckmann Bulletin, No. 0-2016.
Mohan Rao, A.M. & Netravalkar, A.J. Estimation of CC
hydrocarbons in air by pre-concentration on silica gel at dry
ice temperature. Chromatographia, 1986, 183-86.
OSHA concentration limits for gases. FOXBORO Analytical,
USA, MIRANFOXBORO CFR 2206, 1983.
Gas detection limits of B & K gas monitors using various
filters. M/s Bruel & KJaer. Denmark, 1990.
Wood, M.J. Central atmospheric monitoring system for
submarines. J. Nav. Engg, 1990. 32(2), 207-14.
Ewing, G.W. Instrumental methods of chemical analysis.
McGraw Hill Kogakusha Ltd, Sydney, 1975. pp. 412-37;
Instrumentation Ltd, Kota, 1977. Technical pamphlet
Thermacon 4 T. TCD analysis Data Sheet 21-1-11 en.
Vogel, A.I. Practical inorganic chemistry. Longmans Green
Co., London, 1972, pp. 565-69.
Werner Schaefer. Methods and principles of H & B analysers
for gases and liquids. Seminar on Gas Analysis & Pollution
Monitoring, Instrumentation Ltd., Kota, 1977. pp. 17-22.
MINOS atmospher ic oxygen monitor. Beckmann
Instruments Inc, Advanced technology operation, Aratheim,
Ca, USA, 1974. Beckmann Bulletin, No. 0-2016.
83
84
18.
19.
20.
21.
22.
23.
MSA technical pamphlet, Kolkata, India, 1982. Mine Safety

Appliances (India) Ltd. Kolkata.
Manahan, S.E. Environmental chemistry. Willard Grant
Press, Boston, USA, 1983, pp. 235-42.
Mohan Rao, A.M. & Pandit, G.C. Concentration profiles of
hydrocarbons in Bombay, Presented at 2nd National
Symposium on Environment, Defence Laboratory, Jodhpur,
Paper No. NSE2/93121, 1993.
Stern, A. Air pollution, Vol II; Analytical Methods, Vol III,
Academic Press, New York, 1977, pp. 202-204.
Rao, M.V.R.K.; NSTL technical report, DRDO, 1974,
pp.1-14.
Short D.W.E. & Wheatley, K.H. The determination of stibine
in air. J. Royal Naval Service, 1962, 11(2), 65.
CHAPTER 9
SOME CONCEPTS OF AIR POLLUTION
CONTROL IN SUBMARINES
Strategies for controlling pollutant levels inside the
submarine compartments are generally contemplated in three ways:
Metabolic process control, in which one can envisage the
reduction of carbon dioxide content in the atmosphere by
logistically restricting the number of men at work.
Operations control, wherein pollutant generation can be arrested
at the source itself.
Air cleaning process, which utilises the techniques of absorption,
adsorption, filtration, electrostatic precipitation, combustion, etc.
By adopting one or a combination of these strategies
one can ensure the reduction of pollutant. These concepts are
discussed in detail in this chapter.
9.1
METABOLIC PROCESS
It is seen from Chapter 2 that the habitability in
submarine poses a problem of carbon dioxide flux as well as
hypoxia. It was discussed therein that the generation of carbon
dioxide in the cabins is directly proportional to the number of
men and the type of work. A man under normal circumstances of
work generates 25 litres of carbon dioxide(CO2) per hour. It is
therefore imperative that for achieving pollutant reduction, it is
necessary to define the targets of work, which men are expected to
perform and deploy only the exact required number of personnel on
board. Depending on the tonnage and the functions of submarine,
this number changes. On an average 40 persons are present on
board.
A reduction in CO2 level is possible after introducing
certain amount of automation in submarine operations. If we
assume that in a nuclear submarine where power supply is
abundant, if one achieves automation to the extent of 30 per cent,
86
then it leads to a reduction of CO2 to at least 25 per cent.

The concentration of suspended particulates present in
the submarine is also directly proportional to the number of men
and duration of cruise. It has already been stated earlier that on
an average 0.4 mg/m3 of SPM is built-up during 100 hr cruise. In
addition, body odours also become prominent when large number of
persons operate in restricted areas.
An increase of 10-20 fold in condensation nuclei and in
the number of positive and negative ions in the air of conventional
fleet submarines during submergence was also observed by
Schaefer 1.
Production of ammonia, body odour (acetone plus 0.03 per
cent urea plus 0.001 per cent butyric acid in sweat), saliva and
other metabolic products have also been linked to the presence of
crew in submarine. All types of these metabolic-generated
contaminants can be controlled by suitably restricting the essential
number of persons for work.
9.2
CONTROL OPERATIONS
Some of the operations wherein the contaminants can

be ingeniously controlled at source itself are shown in Table 9.11-3.
Table 9.1. Operations during which pollutants are generated
on board submarines
Operation
Battery discharge
Escape
MEA scrubbing
Fast surfacing
Panelling
Duration
(min.)
600
60
120
few min.
-
Pollutants
Range
H 2,SbH 3,H 2SO 4,H 2
0-4%
SbH 3
H2SO 4
0-2 ppm
0.01-2 mg/m3
Cl2
Not known
MEA
-do-
N 2H 4
-do-
HCHO
-do-dosee Table 2.12
Heating/cooking
foods
Smoking cigarettes
Degreasing metal
30
5
Acrolein
SPM, PAH,
surfaces
15
CFCs
Mercury spillage
Freon leak
if unnoticed, Hg
eternal
-do-
CFCs HCl
Not known
1000 ppm
These processes are described in detail in Chapter 2.

However, a brief account is given below:
Some Concepts of Air Pollution Control in Submarines
(a)
(b)
(c)
(d)
(e)
(f)
To reduce the level of pollution during battery discharge

operation of the submarine, it is necessary that health of the
battery system be inspected from time to time. When the
batteries are introduced the generation of pollutants is far
less than when they become old. The acid quality and the
lead plates grid have to be examined periodically.
The escape of men from a submarine in distress is a very
skillful operation. The person reaches the escape chamber
wherein he wears the jacket and manoeuvres into the
torpedo tubes for final bailout. Since the environment in this
chamber does not cater for enough oxygen, the oxygen candle
in the jacket has to be operated for the supply of oxygen.
During generation of oxygen from the chlorate, a small quality
of elemental chlorine comes out. Care has to be taken to
eliminate this gas by in situ absorption by barium oxide
present in the candle, otherwise accumulation of chlorine
occurs. The performance characteristics of the oxygen candles
have to be checked periodically.
Monoethanolamine (MEA) vapours emanate from scrubbers
in the compartments of nuclear submarines. MEA is the
effective material used for absorbing carbon dioxide present
in cabins, and it gets regenerated on heating with steam in
the same container. The contamination of cabins with MEA
thus regenerated can be controlled effectively by operating
the scrubbers at comparatively low temperatures, and placing
traps for holding outgoing vapours.
Fast surfacing of a submarine is a manoeuvring operation.
The principle involved in this operation is that a sudden
emergence of nitrogen gas obtained from reaction of
hydrazine and nitric acid (oxidant) pushes the submarine
from deep depths to the surfaces within 20 s, which is
otherwise not possible. Under these conditions, vapours of
hydrazine enter the cabins and cause contamination. The
level of hydrazine is first checked and it is removed by
filtration of air through oxidant-impregnated active carbon.
The risk of formaldehyde contamination of cabin air arises
from the use of phenol-formaldehyde resins employed for
panelling surfaces. It has been established that formaldehyde
is toxic beyond 0.3 ppm in air and hence the use of these
panels on board be minimised.
Although heating and cooking of foodstuffs, fatty materials
on board is not practised, yet sometimes this occurs, leaving
acrolein and aldehydes into the atmosphere. The load of these
87
88
(g)
(h)
(i)
(j)
organic compounds in air is to be reduced cautiously by

adapting to more tinned foodstuffs.
Cigarette smoking leads to occurrence of nicotine and
polynuclear aromatic hydrocarbons compounds accumulation
in air. Prohibition of cigarette smoking alone enables the
control of these toxic pollutants.
The use of degreasing solvents, polishes and paint removers
while the submarine is on cruise has to be avoided to reduce
the loading of atmosphere with several chlorohydrocarbons.
When thermometers containing mercury are broken
accidentally causing spillage of this metal, slow vaporisation
occurs (Appendix A). Special care has to be taken to control
the pollution caused by this incident by physically removing
the droplets of mercury from the ship and disposing it off
outside.
Refrigeration operation as well as firefighting material and
their storage leave vapours of freons into the atmosphere.
Freon digestors destroy these materials by burning and
producing hydrogen chloride instead, which is subsequently
trapped by scrubbers. Periodical inspection of freon cylinders
and firefighting compound tanks, and valves will ensure
avoidance of freon leaks.
REFERENCES
1.
2.
3.

J. Naval Engg, 1990. 32(2), 215-29.
purification equipment. Presented at symposium on naval
submarines. IKL, Lubeck, 1983.
Gabler, V. Submarine design, Chapter IVGeneral
description of a submarine. Inginier kontor Lubeck, Prof.
Gabler Nachf. GmbH, 1978. pp. 30-35.
CHAPTER 10
AIR REVITALISATION IN SUBMARINES
The concept of air revitalisation in closed spaces is
particularly applicable to submarines and spacecraft. The crew in
these compartments work under adverse conditions and need a
clean environment. Men working in sealed cabins of submarine
gradually consume oxygen and release carbon dioxide into the
atmosphere. They also produce metabolic products, such as sweat,
saliva, faeces and dirt, which contaminate the pure air. Operating
machinery, cooking, smoking and battery operations produce gases
and aerosols that are toxic to human beings. A list of these
compounds present in submarine compartments is given in
Appendix E. Air revitalisation, is thus, the summation of a series
of operations in the environmental management of a submarine,
which cover the removal of toxic air pollutants and at the same time,
addition of vital constituents, thereby maintaining a reasonable
environment for living. The systems which help in maintaining
this environment are known to be life support systems. Air
revitalisation is different from air exchange (with fresh outside air)
in the sense that the same air volume with its constituents
already present has to be managed after purification through the
application of modern technologies1.
The sub-systems under air revitalisation are categorised
as follows:
Atmospheric composition and pressure control

Oxygen supply
Carbon dioxide control
Hydrogen and carbon monoxide elimination
Organics and trace contaminants removal
The parameters to be considered are:
Free volume of air in submarine
Crew number
90
Mission duration, e.g., 12 hr, 24 hr, 90 days or more

Existing main pollution control systems and the
auxiliary systems
Stowage of materials, risks, etc
Design of the existing pollution control systems and

subsequent improvements (modern technologies)
Automation
The composition of air in submarine compartments, to
start with, is the normal air with the following:
Gas
Nitrogen
Oxygen
Argon
Carbon dioxide
Other gases
Per cent by volume

78.05
20.90
0.93
0.03
0.09 (including water vapour)
The partial pressures of oxygen and carbon dioxide inside

cabin air are 137-160 mm mercury and 1.5 mm mercury,
respectively. This corresponds to 18-21 per cent of oxygen and below
0.2 per cent carbon dioxide. Now, as the crew members inhale the
air containing oxygen, its concentration falls steadily, and fresh
supplies of this gas have to be introduced to maintain the pressure
of cabin air. This is effected in three ways:
This method is commonly employed in all submarines.
It consists of dual metering valves and flow meters. The metering
valves can be manually adjusted to allow required quantities of
oxygen into the forward or aft compartments and the partial
oxygen pressure periodically monitored. The change in partial
pressure of oxygen when no addition is operated, is usually around
0.76 mm mercury per hour, which is rather very slow. On the whole,
manual control is quite reasonable though it needs personal
attention.
This is achieved by means of an oxygen sensor signal
given to the supply system lever. The sensor can be a mass
spectrometer also, as positioned in the present day nuclear
submarines. Alarms also are positioned. This is cost-effective to
at least 30 per cent.
Any of the above techniques can be employed to
maintain cabin pressure and composition of air. There are several
techniques for generation of oxygen in enclosed spaces, as well
as to absorb carbon dioxide and other released contaminants.
Typical description of these is given in ensuing paragraphs.
Air Revitalisation in Submarines
10.1
OXYGEN SUPPLY
Presently, several techniques are available to maintain
the life support level of oxygen (21 per cent) in the enclosed
compartments of submarines2, 3. Table 10.1 gives a cursory account
of these techniques. Majority of the conventional submarines
employ HP gas storage oxygen, LOx or potassium superoxide
cartridge or a combination of these techniques. Electrolysis and HP
gas storage are adopted in the nuclear-powered submarines. For
escape operations, all submarines have to resort to oxygen from
oxygen candles alone4. A brief account of each of these is given
below:
Table 10.1. Oxygen addition
Type
Principle
Merits
Demerits
Remarks
Potassium Reaction with

superoxide CO2 and water
present in air
liberating O 2
Compact;
High cost;
removes CO 2 hazard problem
organics,
storage on board
odours
as well
Widely
employed
in submarine,
precautions to
be taken
Oxygen
candle
Chemical
reaction
Efficient,
compact,
stable at
room
temperature,
no power
requirement
low risk
O 2 supply
is oncethrough,
possible
Cl 2 liberation
as well
Eminently
suited
for escape
operation
as in
damaged
submarine
LOx
Physical
storage
at low
temperature
Cheap and
reliable
technologies
available
Volume and
shape of
tank determine
safety precautions
to be followed.
Used in
submarine
and
spacecraft
Pressure
vessels
Physical
storage
at normal
temperature
Cheap
and
reliable
Volume and
Used in
weight of pressure subvessels determine marines
safety precautions
to be followed
Electrolysis
of water,
HP
Ionisation
of water and
generation
of oxygen and
hydrogen
Cheap and
reliable,
large space
Power
requirement;
hydrogen
bottling
Solid
polymer
electrolysis
-do-
Cheap and
Powe r
reliable,
requirement
continuous
high technology
supply; small
space required
Convenie ntly
used in
submarines
Currently
used in
submarine
and
spacecraft
91
92
10.1.1
High Pressure Gas Storage

Oxygen requirements of the mission are to be calculated
and carried on board at the start itself in the form of high pressure
gas cylinders. The supply of oxygen into the cabins is manually
regulated from cylinders, which do not require power, waste
management and are not a safety hazard except that they occupy
space. For conventional submarines, which cruise 20 hours a day,
this oxygen supply is adequate and reliable.
10.1.2
Liquefied Oxygen
Storage of oxygen on board in the form of high density
cryogenic fluid or as liquid-vapour in compact lightweight containers
at a temperature of 162C and at high pressure levels of 900-1000
psi affords a reasonable supply of oxygen to the crew. When oxygen
comes out of the cryogenic tank, it is at a temperature of 250 F,
and therefore, must be heated before it enters the distribution
system. Presently, this technology is highly perfected and widely
accepted for air revitalisation in submarines.
10.1.3
Chlorate Candles
Oxygen generation through sodium chlorate (NaClO3)
at elevated temperature is another technique for air
revitalisation in the closed atmosphere of a submarine. The
chlorate candle consists of a mixture of sodium chlorate, iron
powder, barium peroxide and a small quantity of fibrous binder.
The top end of the candle has a high content of iron powder,
and energy is applied to this segment when ignition occurs. The
flow of oxygen is to the extent of 2 m 3 and is steady over a period
of 70 minutes. No extra energy is required for distribution of
oxygen after ignition. The iron combines with some of the oxygen
to produce oxides, which produce enough heat for the process to
be self-sustaining.
2NaCl + 3O
2Na ClO
3
2Fe + O2
2FeO
BaO2 + Cl2 O2 + BaCl2

The oxygen generated is accompanied by small quantities
of chlorine, salt (aerosol), carbon monoxide and carbon dioxide. Any
chlorine that is generated is trapped by barium peroxide.
Chlorate candles are fitted in conventional as well as
nuclear submarines and perform excellent jobs especially when
the ship goes sick or is distressed. It is also used in the escape
path of the submarine where oxygen is needed. A standard candle
(in cylindrical form, 380 mm high, and 114 mm in diameter) meets

all the oxygen requirements in any submarine.
10.1.4
Potassium superoxide reacts with water and carbon
dioxide present in compartment air and releases significant
quantity of oxygen 5. Each pound of this oxide is capable of
generating 0.3 pound of oxygen under normal circumstances in
closed spaces.
The design of the superoxide plate array is such that it
is positioned near a fan, which blows contaminated air into the
array, and at the other end pure oxygen flushes out with air.
These are proven systems in the conventional submarines for
oxygen generation.
(a) Oxygen generation process
4KO2 + 2H2O 4KOH + 3O2
4KO2 + 2CO2 2K2CO3 + 3O2
(b) Carbon dioxide absorption
2KOH + CO2 K2CO3 + H2O
KOH + CO2 KHCO3
10.1.5
Oxygen Supply from Water Electrolysis

Electrolysis of water dissociates it into the basic
elements, namely, hydrogen and oxygen and this is a sure source
of oxygen supply in submarines. Pure water is not good conductor
of electricity, and therefore, either alkaline or acidic electrolysis
is performed using cells. High pressure electrolysis of water
containing 38 per cent KOH is performed in an electrolytic cell under
35 bar (pressure generated by nitrogen) in an automatic system
to generate pure hydrogen and oxygen. Oxygen production can be
increased with a high current setting. A transformer-rectifier unit
of a submarine electrical system supplies the necessary DC power
for this electrolysis. In the cell, migration of OH to the anode

+
takes place and K to the cathode on application of electric current.
The OH gives up four electrons and oxygen by the equation
4OH > 2H2O + O2 + 4e
(1)
The water takes up the 4e in turn and forms hydroxyl

ions and molecular hydrogen
93
94
4H2O + 4e 4OH + 2H2
(2)
Summing up Eqns (1) and (2), we get

electrolysis
2H2O 2H2 + O2
In the process, however, net enrichment of KOH
concentration in cathode side occurs (i.e., increase from 38 to 44
per cent in concentration) and depletion of electrolyte
concentration at anode site. The process is automatic and can
be shut down in emergency following certain operation
procedures2.
10.1.6
Solid Polymer Electrolysis

The concept of solid polymer electrolysis (SPE) for
oxygen and hydrogen was first generated at NASA, USA.
Subsequently, the General Electric Co. worked on this and
brought out a viable energy system. This has been used in
spacecraft by NASA. In 1979, CJB Instrumesnts Inc, UK,
developed an SPE system for native use and export 2.
SPE replaced the erstwhile alkaline electrolyser (HP
type) in nuclear submarines because of its many advantages.
These are:
Simplicity
No requirement of pressure vessel for electrolysis
Operational problems associated with HP pump,

maintenance of electrolyte level, etc are minimised
Constant generation of required oxygen or hydrogen
Minimum quantity of gas stored in cell

The specific disadvantages of the SPE system are:
Largesized plant
Requirement of compression of hydrogen before discharge.

However, it is worthwhile to note that the advantages
overweigh the disadvantages, and thereby, the system was
recommended for supply of oxygen in closed spaces of spacecraft
or nuclear submarines where power supply is not a constraint.
Basic construction: Unlike normal electrolyte in a cell, in SPE, a
synthetic perfluorosulphonate film, which belongs to the category
of conducting polymer, comprises the electrolyte. The anode and
the cathode, which are noble metals, are clad on either side of the
film and the total assembly constitutes an electrolytic cell.
The polymeric material is a PTFE type in which
sulphonate (SO3H) groups are bonded to the carbons. The
structure of the material is rigid, tough and permeable to water,
thereby offering good environment for electrolysis. The cations
move on freely and permeate through this. The polymeric material

is currently marketed under the trade name Nafion by Du Pont,
USA/Japan.
Process: A schematic design of an SPE is shown in Fig. 10.1. Pure
water is fed through the anode side of the SPE and is decomposed
at the anode liberating oxygen and hydrogen ions.
2H2O + 4e O2 + 4H +
(1)
The H+ migrate through the SPE to the cathode side

under the influence of a potential gradient between anode and
cathode and are discharged at the cathode, liberating
hydrogen gas.
4H + + 4e 4H2
(2)
On account of the direct cladding of large surfaced anode

and cathode plates to the highly conducting SPE, it is possible to
apply high current and, produce more oxygen. Minimum electric
overvoltage and resistivity are also ensured. The cell is very
compact and does not require any corrosive acid or alkali for
conduction of water. After electrolysis, oxygen is taken into the
environment through a ventilation system and hydrogen is passed
into a diaphragm compressor and bottled.
The control of electrolyser is automatic. When required,
the rectifier is switched on to give appropriate current. The desired
HYDROGEN COLLECTOR
HYDROGEN
OXYGEN TO CABIN
OXYGEN
MEMBRANE
ELECTRODE CLADDING
WATER IN
Figure 10.1. Sketch of an SPE oxygen generator
95
96
oxygen concentration is reached within a short time and purity of

gas is monitored periodically by means of gas analyser. The whole
process is simple. Currently, SPE system is fitted on board nuclear
submarines for uninterrupted supply of oxygen to crew. The
hydrogen, which is generated in this system can be used in the
fuel cells, heaters, etc. on board.
10.2
HYDROGEN ELIMINATORS
A hydrogen eliminator operates in the submarine when
the ship is underwater. Hydrogen is generated from batteries and
its release is dependent on temperature, age of the battery and
duration of its operation. In the eliminator, hydrogen is oxidised
in the atmospheric air over a surface of palladium catalyst to water,
while the catalyst is maintained at a temperature of 315C.
The catalyst is a palladised alumina pellet, which is
packed in a fine nickel or monnel metal wire gauge envelope carried
on two parallel brass tubes in the eliminator case. The casting is
open at the top and bottom to allow free flow of air. The brass tubes
contain small heaters, which are wired in series and connected to
a junction box. The heaters perform the job of maintaining a
suitable temperature for the conversion of hydrogen into water even
at very low ambient concentrations and also to dispel any water that
might have condensed in the eliminator casing. A thermometer
is fitted to one side of the eliminator to indicate the temperature.
The eliminator operates on the thermal convection of air current
set by the burning of hydrogen and so do not require any fan. The
siting of the eliminator is a little away from the hull to allow free
space for air current and diffusion of hydrogen.
The heater units are switched on at the time of sealing
the submarine ventilation and are put off only after the submarine
has been opened up for outside air ventilation. The eliminator
should invariably be switched off at the time of battery charging as
other gases and vapours would spoil the catalysts. The eliminator
can remove 7 cu ft of gas per hour for a 2 per cent concentration of
hydrogen in the chambers 6. The quality control and periodic
performance monitoring (monthly) has to be followed very
scrupulously.
10.3
CARBON MONOXIDE CONVERSION

The toxic gas, carbon monoxide, is present in enclosed
spaces of submarine only on account of cigarette smoking and
burning of alcohol fuel. Since low concentrations of this gas are
also not tolerated inside the submarine, this is eliminated together

with other unsaturated organics, carcinogens, etc. by passing air
through a catalyst bed containing hopcalite or metal oxideimpregnated active carbon 7. Hopcalite is a mixture of oxides of
manganese, copper, cobalt and silver in different proportions 8.
Hopcalites have high oxidising capacity at ambient and elevated
temperatures. Metal oxide-impregnated active carbonsalso a
special catalyst preparation convert many unsaturated/saturated
organic substances (including carcinogens) into less harmful
substances, which are subsequently held up on carbon filters.
Typical preparations of a hopcalite and metal oxideimpregnated carbon are described here.
10.3.1
Hopcalite
For the preparation of hopcalite catalyst, fresh lots of
manganese dioxide and copper oxide are prepared. Manganous
sulphate in distilled water is treated with sufficient quantity of
sulphuric acid, cooled and then treated with solid potassium
permanganate to afford a precipitate of manganese dioxide. The
precipitate is washed free of sulphate and kept aside
(yield = 85percent). Similarly, copper oxide is precipitated by
addition of copper sulphate pentahydrate in distilled water to a 30
per cent sodium hydroxide solution with constant stirring and
passing steam to maintain the warm temperature. At this stage,
copper oxide is precipitated (yield 35 per cent). For preparation of
hopcalite catalyst, the wet precipitate of both MnO2 and CuO are
mixed in 3:2 ratio and agitated with stirring. On filtration in a
Buchner funnel, a cake of the catalyst is obtained, which is suitably
kneaded, freed from water by applying pressure between filter paper
pads, and later dried at 120C. The dried mass is crushed and
packed in sealed containers.
The apparent density of hopcalite is 0.6 g/cc and real
density 3.01 g/cc, which compares well with similar imported
preparations. The carbon monoxide conversion to carbon dioxide
is about 90 per cent.
10.3.2
Metal-Impregnated Active Carbon

Active carbon prepared from coconut shells using an
indigenous process developed at the Indian Institute of Chemical
Technology, CSIR, Hyderabad, was chosen as the support material.
The two metals usually impregnated are copper and chromium.
Method: A sufficient quantity of activated carbon is degassed at
150 C, and then cooled under vacuum in a rotatory evaporator.
97
98
Copper salt solution was prepared by dissolving basic

copper carbonate and ammonium carbonate in liquid ammonia to
afford a concentration of 130 mg of Cu/ml.
Impregnated copper active carbon catalyst was prepared
by the addition an aliquot of the above prepared solution to the bed
of degassed carbon. They were heated at 150C for 2hrs in an oven
and then stored in sealed bottles.
The metal concentration of impregnated carbon is
determined by leaching each category with 50 per cent HCl
completely and determining the leached metal by volumetric
methods. Typically, 9.4 per cent wt/wt of Cu, 5.0 wt/wt Cr and
8.01 Cu + 2.8 Cr in mixed metal (4:1) contents of metal are
prevalent in these preparations.
10.3.3
Activated Carbon
A physically active form of carbon, known as activated
carbon is widely employed in the pollution control work, especially
in submarine environment. Basically, active carbon possesses
high internal porosity on account of which it will absorb chemicals
in either liquid phase or gas/vapour streams 9.
Surface area of active carbon is an important parameter,
which is determined by pore diameter. It generally possesses a
pore diameter of 3 nm and below for gas/vapour phase adsorption
and 3 nm and above for liquid adsorption. Generally, gas/vapour
phase adsorptive types of activated carbons are hard granules and
those of liquid phase are granular or powder forms. The properties
of these two types are indicated in Table 10.2.
Table 10.2. Physical properties of different active carbons
Property
Liquid phase type
Mesh (mm), Tyler

CCl4, activity
Iodine no. min.
Bulk density
(g/ml.min.)
Ash % max.
Wood
base
100
40
700
0.25
7
Gas phase type
Bitumenaceous
coal base
8-30
50
950
0.50
Coconut
shell
6,+14
60
1000
0.50
Coke
6,+8
60
1000
0.52
2
The ASTM test methods for activated carbons are:

Apparent density
D 2854
Moisture
D 2867
As h
D 2866
Particle size distribution
D 2862
Liquid phase evaluation
D 2855
Manufacturing process: Nearly all organic substances of animal,

plant or mineral origin can be converted into activated carbon by
these processes (Regional Research Laboratory, Hyderabad9).
Process 1: Carbonisation in raw material stage and addition of
chemical to dehydrate/degrade during calcination.
Process 2: Carbonisation and selective oxidation of the carbon
matter with air or steam or flue gases to get the desired
active carbon.
The carbons from nutshells are first carbonised then
followed by crushing to size and activating the mass directly to give
hard dense granules. Alternatively, raw materials, such as coal or
coke is crushed to powder, formed into briquets or pellets with a
tar or pitch binder, crushed to size, calcined at 500-700C and then
activated with steam or flue gas at 850-950C to give a uniform
channelled active carbon. Horizontal tunnel kilns and vertical
retorts are used in these processes. The quality of the carbon is
chemically indicated by pH, ash content and CCl 4 or benzene
absorption capacity.
Gas absorptive capacity of an activated carbon is
determined dynamically by blowing a test gas through a carbon bed
or a standard tube of specified depth and diameter and establishing
the saturation of carbon with vapour/gas. The weight per cent
pickup of the vapour-gas indicates the gas absorptive capacity.
Metal-impregnated active carbons are the transformed
types. They are prepared by mixing metal salt with active carbon
followed by dehydration and activation. Their special types, which
exhibit the properties are described under Section 10.4.2. Gas
purification is achieved using active carbons. Vapours released
from paints, solvents, fuel oils, smoking, cooking, metabolism
products and sewage systems inside the submarine are eliminated
by passing the air through the filters packed with activated carbon
(coconut shell based) kept near the air-conditioning and
sewage systems.
10.4
CARBON DIOXIDE CONTROL

The need to control carbon dioxide in naval and nuclear
submarines arises after a dive of about 7 hrs during which time
its level reaches the MAC. After this period, if the submarine does
not desire to snort, some sort of carbon dioxide elimination process
has to be started. For this purpose, many processes have been
developed from time to time and these are described already in
Chapter 9 and shown in Table 10.3. The specific materials used
in these processes are also described herein. By eliminating excess
or undesirable quantities of carbon dioxide in submarine, one will
achieve air revitalisation.
99
100
Table 10.3. Carbon dioxide absorption systems
Type
Principle
Merits
Demerits
Sodalime
Chemical
reaction
with CO2
affording
Carbonates
-do-
Low cost,
effective at
low temperatures
Bulky, low
efficiency
Nonregenerative
type
Very efficient
at all temperatures
High cost
-do-
Potassium -dosuperoxide
Very efficient, High cost

low power
Storage
requirement.
hazardous
Oxygen is
also liberated
simultaneously
-do-
Monoethanol amine
Chemical
reaction
reversible
Low power
requirement,
Efficient
High
toxicity
Spillages
Regenerative
type
Solid
amine
Chemical
reaction
Efficient
Storage
Space
requirement
Steam
requirement
-do-
Molecular
sieves
TSM
Electrostatic
attraction of
CO2, and
sieving of
other
molecules
Efficient
Low cost
Small
space
requirement
Pre-moisture
elimination
from air is
a requirement
Regenerative
any number
of times
PSM
-do-
Efficient
low cost,
small
space
requirement
Rapid plant
recycling
High power
requirement
for pressure
control
as well as
regeneration
-do-
Lithium
Hydroxide
10.4.1
Remarks
Adsorption on Molecular Sieves

Molecular sieves are chemical compounds of the
general formula M2/nO.Al2O3 YSiO2.WH2O. Where, Y is 2 or greater,
n is the cation value and W the water contained in the voids of the
sieve chemical. These microporous chemicals with uniform pore
sizes in the range 0.3-1.0 nm or 3-10 can selectively adsorb or
reject molecules and are thus denoted as molecular sieves. The
adsorption capacity of molecular sieve is due to electronic forces
between the adsorbent and adsorbate. Also the sieves can be

regenerated and got rid of the adsorbate completely on heating to
about 300 C for 2 hrs.
10.4.1.1
Preparation
A typical preparation of synthetic molecular sieve from
starting materials, e.g. freshly coprecipitated or amorphous reactive
solids, alkali metal hydroxide or strong base, such as tetra alkyl
ammonium hydroxides, is described here.
A gel is prepared from the reactive starting materials
under low temperature hydro-thermal conditions and a high degree
of super saturation of the gel components leading to the nucleation
of a large number of crystals. The gels are crystallised in a close
hydrothermal system at temperatures varying from 20 to 200C
from few hours to days. The aluminosilicate gels when prepared
are in appearance ranging from stiff translucent to opaque
gelatinous precipitates and heterogeneous mixtures of amorphous
mass dispersed in aqueous solution. The scheme of gel preparation
is shown below:
NaOH (aq) + Na Al(OH)4 (aq) + Na2SiO3 (aq)
[Naa(AlO2)b(SiO2)c.NaOH.H2O] gel
Nax [(AlO2)x(SiO2)y].m H2O + solution
= Molecular sieve
The temperature strongly influences the crystallisation
time, and as the temperature is high, time taken for crystallisation
is low.
The hydrogel to zeolite amorphous powders is mixed
with clay, blended and extruded into pellets and dried to give
molecular sieve. In this process, the raw Kaolin component is then
converted to metakaolin and crystallised to Zeolite A to form a
preformed pellet.
10.4.1.2
Identification
Each Zeolite is characterised by its X-ray powder
diffraction pattern and for its quality in a catalyst composite.
Standard chemical analysis and thermal analysis are also followed
for quality control.
10.4.1.3
Adsorption characteristics
Oxygen adsorption at low temperature (183 C) is
employed for determining the Zeolite content. In a McBain-Baker
type of gravimetric microbalance, this experiment is performed with
a degassed (350-450 C/10-5 mm Hg , 9-16 hr) sample.
101
102
10.4.1.4
Tailored MS
It is possible to tailor the zeolite adsorption
characteristics in terms of size selectivity, including cation
exchange, cation removal, etc. These changes offer wider
applications in separated ions. Also, zeolites have a high affinity
for water and other polar molecules in the drying applications. The
properties of several types of commercial molecular sieves used
in industrial applications are recorded in Table 10.4.
Table 10.4. Physical properties of molecular sieves
Physical
Form
3A
4A
5A
13X
AR
Available in 1.5 and 3 mm dia cylindrical pellets in general
Pore dia.
Bulk density (gm/lit)
3
740
Crush strength for

3mm dia pellets kg
Loss on attrition
4
650
5
650
10
530
600
less than 0.5%
Equilibrium
21.0
24.0
adsorption
capacity for H2O at
30 C and 75 % RH
(Internal surface area 700-800 sq m in general)
19.5
2.6
12
(60 % RH)
Source: ACC technical paper.
Process cycles: Two processes, namely, temperature swing and

pressure swing are usually applied for the separation of impurities
in gases or air. These have wider applications in the air purification
in submarines (e.g., to remove CO2). More details are given in
individual illustrations.
10.4.1.5
Temperature swing molecular adsorption process

In this process, the air laden with carbon dioxide is
adsorbed on molecular sieve -(4A) type bed at rather low temperature
in an absorption system. Side by side on heating similar molecular
sieve beds and applying vacuum, the carbon dioxide is released and
compressed onboard in bottles. Just before adsorption of carbon
dioxide on molecular sieve bed, water vapours in the air have to be
preadsorbed on either molecular sieve-3A bed or dried silica gel bed
in order to allow the molecular sieve-4A beds full capability for
carbon dioxide adsorption. Carbon dioxide and hydrogen are
eliminated later by oxidation. TSMA is already in use onboard
nuclear submarines.
10.4.1.6
Pressure swing molecular adsorption process

Pressure swing molecular adsorption (PSMA) involves
pressure cycling so that adsorption occurs at rather high pressures
and desorption achieved on lowering the pressure and purging with

carbon dioxide free air. In practice, several problems are
encountered, namely, co-adsorption of water and carbon dioxide
and difficulty in the removal of water vapours and non-availability
of a specific adsorbent exclusively for carbon dioxide, etc. One great
advantage PSMA offers, is a rapid cycled process at low
concentration loading (of carbon dioxide) on beds and hence can be
operated at pressures close to ambient, and a number of cycles can
be completed in shorter duration as compared to TSMA. However,
in a multi-stage PSMA, some of the difficulties were overcome and
a reasonably workable process has been developed. This works
according to three stages:
(a) Water removal: Inflowing air freed from dust and oil is
compressed to approx. 2 bar and passed through a dried silica
gel bed for affecting water removal.
(b) Carbon dioxide concentration: The dried air stream at the
same pressure is passed through one or more molecular sieve-4
beds until all carbon dioxide is adsorbed. The main air flow
subsequently is returned to the silica gel regenerating bed of the
first stage for passing into the environment.
As the carbon dioxide adsorption process proceeds,
regeneration of carbon dioxide from the molecular sieve-4 beds
go on at reduced pressure (by applying vacuum) together with
purging dry carbon dioxide free air, and the carbon dioxide thus
released is concentrated to as high as 25 per cent in several cycles
automatically. The molecular sieve-4 beds are regenerated for
further usage.
(c) Carbon dioxide separation and offloading: In this stage, the
carbon dioxide is separated effectively by readsorption of the
carbon dioxide rich air mixture over molecular sieve-4 beds and
taking-off the pure air to the first stage in the environment.
Consequently, the regeneration of these molecular sieve-4 beds
at this stage is achieved again by low pressure applied through
vacuum. Full scale working PSMA prototypes are fitted on board
submarines and are effectively controlling carbon dioxide pollution
in the cabins.
10.4.2
Sodalime
Sodalime is the most common absorbent placed in
canisters for removing carbon dioxide from cabin air. It is a mixture
of sodium and calcium hydroxide whose composition is shown in
Table 10.510.
103
104
Table 10.5. Composition of sodalime
Constituent
Per cent content
Sodium as sodium hydroxide

Calcium hydroxide
3.0
73.9
Magnesium
0.89
Iron
0.2
Silicon dioxide
5.3
Moisture
16-19
Hardness number (min)
70
Source: Indian Standards Institute, 1969.
To start with, carbon dioxide in air reacts with sodium

hydroxide in the liquid phase and is converted into sodium
carbonate.
CO2 + 2 NaOH Na2CO3 + H2O
(1)
The sodium carbonate in solution thereafter reacts with

calcium hydroxide producing calcium carbonate (insoluble) and
sodium hydroxide.
Na2CO3 + Ca(OH)2 CaCO3 + 2NaOH
(2)
Hence, the water content of sodalime in the absorption

process of carbon dioxide is very important. In fact, during
storage, if water content of sodalime falls down it loses its
reactivity and hence these canisters should be kept airtight and
stored at rather humid sites. Under any circumstances, fresh water
should not be directly added into canisters, as it causes lumping
and spoils the product. Also, the flow rate of air through the
canisters play a vital role in absorption efficiency.
10.4.3
Lithium Hydroxide
Lithium hydroxide is also employed in place of

sodalime in canisters for absorption of carbon dioxide in cabin air.
The latest class of submarines use this material inspite of high cost
(40 times) as compared to that of sodalime even at low
temperatures. However, the dusting occurring in LiOH is a
disadvantage factor 11. The characteristics of LiOH, which were
specified by Dornier systems, Freidrischschaefen are given below:
LiOH granules according to DS-ERT-23-79 are useful in

submarines for carbon dioxide absorption.
A cartridge containing 2 g of this material absorbs 640 litres
of carbon dioxide. The air purification system is kept in a
bypass to the ventilation duct.
The material works very efficiently between temperature

range 15-45C and absorpbility increases with temperature. The
humidity conditions at which it is most satisfactory are between
25-90 per cent RH and cabin pressures from 0.8-1.4 per cent and
there is very little pressure drop of air flow in the canisters.
Aluminium should be avoided as a canister casing material. Also
trichloroethylene cleaner should not come in contact with LiOH,
as it is capable of converting it to dichloroacetylene. Since lithium
salts are costly, the resultant lithium carbonate may be offloaded
at shore, where it is recovered.
10.4.4
Potassium superoxide, KO2 is ideally suited to revitalise
the enclosed atmosphere by absorbing the carbon dioxide and at
the same time generating almost an equivalent quantity of oxygen.
It is manufactured on industrial scale in powdered form,
compressed into plates or cylindrical forms and sealed in a metal
array container. During this process, its porosity, mechanical
strength and particle size are maintained intact to allow the free
passage of carbon dioxide into it, and also to afford easy handling.
The following are the chemical reactions that occur when this
superoxide system is put in operation.
4KO2 + 2H2O 4KOH + 3O2
4KO2 + 2CO2 2K2CO3+ 3O2
Theoretically, 1 g of potassium superoxide produces 238
litres of oxygen and absorbs 158 litres of carbon dioxide. Based on
this calculation, the number of systems to be operated or carried
in a submarine are worked out. An added advantage of this
substance is that it oxidises many substances emanating as body
odours, bacteria, hydrogen sulphide, etc., which often get
accumulated in the closed environment of submarines.
The chemical is usually packed in 3 g plate array or
cylinder. The package is very sturdy and does not react until it is
opened. It is not to be kept near fire or smoke. The reaction
efficiency of potassium superoxide is usually 80 per cent. The
material is in use in spacecraft and submarines.
10.4.5
Carbon Dioxide Removal using Wet MEA Scrubber
MEA-based scrubbers are widely used in air purification

processes in conventional and nuclear submarines. The unit draws
power to the extent of about 7 kW for circulating the air for removal
of carbon dioxide in the appropriate system and also to get
105
Source: Clark, A.N. 1990.
AIR OUT
MEA + CO2
MIX IN
CO2 OUT
ELECTRIC
HEATER
REGENERATION
LEVEL
REGENERATION SIDE
POROUS
PLATE
REFLUX
Figure 10.2. Line diagram of MEA scrubber
ABSORPTION SIDE
MEA SLUMP
SYSTEM
MEA FOAM
AIR IN
106
regenerated. Thus, the material revitalises the environment for

the comfort of about 40 persons.
Monoethanolamine HO-H2C-CH2-NH2, (boiling point=
172C) is a liquid commercially available in the country. It has a
high rate of absorption (by reaction) of carbon dioxide. On heating
the resultant liquid product, the carbon dioxide can be expelled out
completely. The carbon dioxide gas thus evolved is passed into a
compressor, then bottled and dropped overboard. A system based on
wet MEA for absorption of carbon dioxide in cabin air is described
below.
The air requiring removal of carbon dioxide is passed
through a filter into the absorption section into a porous plate over
which exists a foam of MEA. The gas comes into contact rapidly
with MEA on foam bed, and the air rid of carbon dioxide is pushed
into water washers and sent out into the system. Side by side,
MEA with carbon dioxide is collected and directed into a
regenerator where it is boiled to expel the carbon dioxide gas into
the compressor chamber and allow the lean MEA to go back into
the absorber section. A schematic design of a wet MEA scrubber
is shown in Fig. 10.2.
10.4.6
Solid Amine Scrubber

A cyclical operation of absorption and regeneration by
solid amine beds was achieved in a system designed for carbon
dioxide absorption based on solid amines. Basically, the solid
amine bed incorporates a high boiling amine supported on a
porous material, which enhances the surface area for absorption
process. Solid amine moiety absorbs the carbon dioxide in cabin
air without the need for prior dehumidification. Screening of
several amines show that strongly basic type of resins having
amino groups absorb carbon dioxide at relatively rapid rate but
has low regenerative capacity on heating. The weak base type
resins possess rather low carbon dioxide absorption capacity but
display greater thermal regeneration. A speciality resin, which is
epoxy-built namely, EPON562 with diethyletriamine has a high
carbon dioxide absorptive capacity as well as the greatest
regenerative character with 20.6 mg carbon dioxide/cc resin/hr
absorption, and 100percent regeneration12.
In practice, a blower in submarine forces the inlet air
containing carbon dioxide through a solid amine bed, which
absorbs the gas and sends out purified air. In the meantime, a
second bed is put for regeneration by expelling the carbon dioxide
from it with the steam-heating and the carbon dioxide is bottled.
107
108
The designs of plants are given by Dorniers (Germany) and Hamilton

Standard, USA.
10.5
FREON CONTROL
The freon contaminated air is let into a pre-heater
where its temperature is raised sufficiently by means of hot
exhaust air from reactor. Thereafter, an electric heater elevates
the temperature of air to about 400C and this hot air is drawn
through a bed of catalyst where it decomposes freons into HCl
and HF on reacting with water vapour.
CCl 2F2 + H2O 2HF + 2HCl + CO2
The gas mixtures are then cooled in stages and then
passed through the sodalime canisters for removal of carbon
dioxide and acid vapours. A freon heater works at a rate of 9.1g
of R 12 removal per week from the environment at a flow rate
of air 20.4 m 3/hr 13.
10.6
AEROSOL REMOVAL
The aerosols in submarine environment arise from
smoking, cooking, high pressure compression and vapour
condensation processes. In addition, sulphate, chloride, copper
and iron are also found in the space.
Air is passed through pre-filters into ESP units through
submarine ventilation system. The high voltage usually 13 0.5
KV (+ve) produces positive ions (in preference to negative ions as
the amount of ozone formed is low) and these charged aerosol
particles are attracted to the grounded plates in two stages
leaving the rest of air into the ventilation channel free from
aerosols13,14.
REFERENCES
1.
2.
3.
4.
5.
Ross, P. & Popina, D. Advanced life support application

study. Final report prepared by Hamilton Standard, USA for
NASA, 1974, under contract No: N.00024-74 C-5477.
purification equipment. Paper presented at Symposium on
Naval Submarines, 1983, London.
J. Naval Engg, 1990. 32(2), 215-29.
Bruty, R.A. Oxygen candlesrecent developments. J. Naval
Engg., 1987, 29(2), 412-14.
Individual survival approaches used for atmosphere
regeneration in submarines. Spiral Marine Technical
Pamphlet No.212.
6.
7.
8.
9.
10.
11.
12.
13.
Hydrogen eliminators. Baird and Tatlock (London) Ltd.

Instruction sheet.
Stern, A. Air pollution, Vol III, 3rd edn. Academic Press Inc.,
New York, 1985, pp. 689-92.
Tech news. United Catalysts Ltd, Bombay, 1990.
Activated carbon from coconut shell. Hyderabad product
news. Hyderabad Carbons Ltd. TOT by RRL, Hyderabad,
1990.
Specification for sodalime. Indian Standards Institution, IS.
1969. 5321-1969.
David, S.H. & Kissinger, L.D. The dependence of the carbon
dioxideRemoval efficiency of LIOH on humidity and mesh size.
A contribution by aerospace division of the American society
of Mechanical Engineers at inter society conference on
environmental systems. San Diego, Calif, July. 1978. 10-13.
Yakut, M.M. Life support system. In Space systems
technology, edited by Heitchne, R.D. Reinhard Book
Corporation, New York, 1996. pp. 171-207.
ESP systems for offices. Crompton Greaves Ltd.
Tech
pamphlet, 1996.
109
APPENDIX A
INDOOR AIR POLLUTION DUE TO

MERCURY VAPOUR
The contamination of air due to vaporisation of mercury
is likely in indoor spaces where work using mercury or its salts is
performed. This is noticed in shops making thermometers, lamps,
compass and barometers, pharmaceuticals and plating where the
spills create a definite vapour pressure. The concentration of
mercury vapours generated at definite temperatures is shown in
Table A.1.
Table A.1
Temperature
(C)
Vapour pressure
(mm)
Theoretical conc. of Hg in air

(mg/l)
(ppm)
20
0.0013
0.0152
30
0.0029
0.0339
4.10
40
0.0060
0.0700
8.5
60
1.84
0.0300
0.3500
100
0.28
3.26
396.0
42.5
200
18.30
213.00
25,800.0
300
246.00
2879.00
3,48,000.0
Source: Jacobs MB, (1949).
Exposure to mercury vapour causes a disease known as

mercurialism, which is noticed amongst the workers handling the
vapours than those handling the salts. The toxic limit of mercury
was fixed at 0.1 mg/m3. All types of mercury, vapours, dust and
compounds are well estimated by Polejaeffs method described here.
Sampling: The mercuricals are trapped from air into an impinger
containing 0.25 per cent of iodine in 3 per cent aqueous potassium
iodide by slowly drawing the air at a rate of 1 cfm. The impinger can
be chosen from amongst 50-150 ml capacity volume. The sampling
solution used in the impinger is made in bulk, usually 1 litre. The
impinged sample is made upto 150 ml using the sampling solution.
112
Standards: A stock mercury solution is made by dissolving

0.135 g of mercuric chloride (HgCl2) in 1 litre of sampling solution.
This corresponds to 0.1 mg/ml, i.e. 100 g/ml. From this stock
solution, another standard solution representing 10 g/ml is
prepared using the same sampling solution. Several optimum range
of standards, namely, 3,4,5,6,7,8,9,10, 15 and 20 g/ml have been
made using the sampling solution*.
Procedure: The 10 g/ml standard (required amount) is placed in
a 50 ml Nessler tube and made upto a 5 ml volume with the sampling
solution. To this 1ml of copper sulphate solution (10percent CuS4
'0'.5H2O in water) is added and swirled. Subsequently, 2 ml of 3 N.
Na2SO3 (75.65 of N2SO3.7H2O in 200 ml water) is added and the
whole mixture is shaken for a while. The precipitate is made to
settle down. A pink colour precipitate indicates mercury, whereas
a white colour one does not signify its presence. Other standards
and sample are also treated in a similar manner and the sample
is compared to the nearest standard. From this, a calculation of
mercury in the sample is made using the equation
where,
C = A X B X D/ E X 141.6
A = Micrograms of mercury found in 5 ml aliquot used for analysis.

B = Volume of impinger sampling solution, including washings.
D = Factor by which impinger sampling solution and washings
are diluted (Thus, if 50 ml are diluted to 250 ml, the factor
would be 5).
E = Cubic feet of air drawn through the impinger at the
standard flow rate 1 cfm. E would equal the time in minutes
for the collection of the sample.
C = Average concentration of mercury in air where the impinger
sample was taken, expressed in mg/m3.
Cold vapour method: The principle of estimation of mercury (in
vapour form) is to allow the atoms of mercury to absorb a resonance
radiation of 253.7 nm generated from a low pressure mercury lamp.
To obtain mercury vapours, a vapours generation system is
designed in which the mercury (II) solution is placed. Carrier gas,
namely, mercury-free air bubbles through this medium to produce
and carry along with it elemental mercury from the solution on to
the absorption cell. There, the atoms absorb the resonating
radiation (253.7 nm) and the detectors render the value of its
concentration in the original solution. These cold vapour AA
spectrometers or otherwise known to be mercury analysers are quite
sensitive, easy to operate and are commercially available.
*
Most metallic salts of mercury are soluble in sampling solution to the extent of
0.2 g/100 ml organicals and metallic mercury are poor solutes.
APPENDIX B
ANALYSIS OF POLLUTANTS USING

CHEMICASSETTE MONITOR
Pollutants in the indoor spaces can be conveniently
monitored around the clock basis using a chemicassette monitor.
The monitor operates on obtaining an electrical signal resulting from
a chemical reaction between the subject pollutant and the reagent
on the chemicassette tape. One to four week's continuous data of a
single pollutant can be recorded and stored in the instrument.
A chemicassette is a highly sensitive and specific type of
reagent tape in which a dry chemical is embedded. For each type of
pollutant a separate tape has to be used. In Fig. B-1 the layout of a
chemicassette monitor is shown. In the actual operation, the
chemicassette is allowed to pass through a sampling window where
it comes in contact with the metered sample stream. The target gas
present in the stream reacts with the dry chemical on the tape thus
forming a stain, which is proportional to its concentration.
Concurrently, a beam of light is reflected off the exposed portion of
the tape and the intensity continuously determined. As the intensity
of reflected light comes down due to stain formation, the reduction
is sensed by a cadmium sulphide photocell as an analog signal and
is converted to digital value on the read-out of the instrument,. Thus,
chemicassette monitor is a physical instrument, which combines
chemical reaction, reflectance measurement and microprocessor readout control and affords a continuous and precise measurement of the
reactive pollutant present in indoor air.
A list of the pollutants that can be monitored by this
technique is shown in Table B-1. The instrument is very compact
(6.5" 17" 18") dimensions, lightweight (20 g), requires low power
and offers the alarm facility also. The samples can be drawn into
the instrument from as long as 100 feet safe distance. The
instrument is rugged, operates in the temperature range of 0-40C
and can be operated during crisis occasions of leakages or explosions
in indoor or confined spaces.
114
CHEMICASSETTE
TAPE
GAS SAMPLING
HEAD
REFLECTED LIGHT
FROM TAPE
OPTICAL
FILTER
CADMIUM
SULPHIDE
PHOTOCELL
TUNGSTEN
LAMP
SIGNAL
MEASURING UNIT
SIGNAL FROM
ZERO CIRCUIT
CHEMICASSETTE
Figure B-1. Layout of a chemicassette monitor

Source: MDA Instruments Inc, Illinois, USA, 1991.
Table B-1. Measurement of pollutants using chemicassette

monitor
Pollutant
TLV (ppm)
Response time of monitor(s)
Ammonia
25
20
Chlorine
10
Hydrazine
0.1
40
Stibine
0.1
10
Hydrogen chloride
10
Hydrogen sulphide
10
10
Nitrogen dioxide
10
Nitric acid
10
Sulphur dioxide
10
Source: M/s MDA, USA Technical Pamphlet.
APPENDIX C
GAS CHROMOTOGRAPHY-MASS
SPECTROMETRIC ANALYSIS
Gas chromatography-mass spectrometry (GC-MS)
technique has now become an important analytical tool in
environmental monitoring of organic compounds. The technique is
a combination of an efficient separation procedure and an
unquestionable identification method. The ingenity of interfacing
suitable types of gas chromatography to mass spectrometer for the
purposes of separation and estimation of environmental organic
samples is thus a great leap ahead.
A gas chromatograph in the GC-MS system separates the
individual compounds and the resolved compound is then led into
the mass spectrometer using a special type of sample injector. In
mass spectrometer, the compound is ionised to form molecule-ion
or fragment-ion on bombardment with fast moving electrons in the
vacuum chamber. Collisions between molecules and fast moving ions
(generated from hot tungsten or rhenium filaments) invariably
produce a large mass of molecule-ions (positive) than negative
ions (which is prevalent in ratio 1000:1). These positive ions are
oriented, collected and subsequently directed according to their
masses using an electromagnet. They are finally detected and an
electric signal generated. In this experiment, those electrons,
which do not collide with molecules are caught in an electron trap.
The molecules, which do not get ionised are removed by high
vacuum, which is in continuous operation. The electron impact
(EI) technique renders molecules to produce molecule-ion and many
fragment ions together, whereas chemical ionisation reduces
fragmentation and affords protonated molecular ion (M+I). These
two techniques are amply incorporated in the present day
instrumentation.
The common types of mass spectrometers in use
alongwith gas chromatographs are: (i) Electromagnetic focussing
spectrometer, (ii) Quadruple mass spectrometer, (iii) Time-of-flight
mass analyser, and (iv) Ion-cyclotron resonance.
116
Construction details of these equipment and the GC

interface attachment are found in many instrumental analysis
text books. Finnigan MAT, the innovators of ion-trap technology
have come up with a variety of mass spectrometers (Quadruple type)
with in-built software package to enhance their capability in
quantitatively analysing complex mixtures of organic compounds
in air. The interpretation of spectrum obtained thereon can be
made for several categories of organic compounds by following the
m/e values and intensity of lines. A line sketch of an
electromagnetic focussing mass spectrometer is given in Fig. C-1.
In addition to indoor air monitoring, GC-MS analysis has
been carried out on the samples collected from photochemical
smogs.
CALIBRATED
LEAK
HOT FILAMENT
2500 V
ELECTRON TRAP
ION GUN
ION BEAM
ELECTROMAGNET
COLLECTOR SLIT
COLLECTOR
Figure C-1.Sketch of electromagnetic focussing mass spectrometer

Source: Ewing, G.W. 1975.
APPENDIX D
PHOTOACOUSTIC SPECTROSCOPIC
ANALYSIS
Photoacoustic spectroscopic analysis (PSA) of air
pollutants is an advancement of the commonly known infrared
spectroscopic analysis. All compounds, which absorb the IR
radiation respond to this analysis. The pulsated infrared radiation
on absorption by molecules of gases or vapours generate
temperature, on account of which the pressure inside the chamber
increases or decreases according to the chopping of radiation, and
an acoustic wave is developed. A sensitive microphone mounted
in the chamber measures these signals. The concentration of the
subject gas is proportional to the acoustic signal. When the optical
filter is changed for different gas, measurement of a new signal
will afford the concentration of that gas, and in this manner one
can selectively measure the concentrations of five different gases
in the 10-3 ppm level. PSA analysis can be carried out with
significantly low concentrations of the gases/vapours in air as
compared to the conventional IR spectroscopic analysis.
Based on these principles, a photoacoustic spectrometer
had been developed by Bruel and KJaer. A line sketch of this
instrument is shown in Fig. D-1. The instrument can be used for
the quantitative analysis of upto five components and water vapours
in the air. Indoor air quality and pollutant measurement at
workplaces, or ambient atmospheres can be accurately determined.
The whole operation is automatic and the data is stored in a
computer built-up along with the instrument. The interferences
due to temperature fluctuations in the cell and compensations for
the presence of water vapours in the air samples are taken into
account. The instrument is also calibrated with known gases.
CHOPPER
WHEEL
OPTICAL
FILTER DISC
MICROPHONE -1
Figure D-1. Line sketch of photoacoustic spectrometer
LAMP
(IR SOURCE)
Source: Bruel & KJaer. 1990. Technical pamphlet.
REFLECTOR
ANALYSIS CELL
MICROPHONE-2
SAMPLE OF
AIR
118
APPENDIX E
MAXIMUM ALLOWABLE CONCENTRATION

OF POLLUTANTS PRESENT IN A
SUBMARINE
Compound
Formula
MAC* (ppm)
Acrolein
Ammonia
Benzene
Carbon dioxide
Carbon monoxide
Chlorine
Formaldehyde
Freon12, 21, 114, 11
Hydrogen
H 2C=CH-CHO
NH 3
C 6H 6
CO2
CO
Cl2
HCHO
Hydrogen chloride
Hydrogen cyanide
Hydrogen sulphide
Hydrazine
Gas, LPG
Mercury
Monoethanolamine
Nitric oxide
Nitric acid
Nitrogen dioxide
Ozone
Pentane, propane
Perchloroethylene
Ph e n ol
Stibine
Sulphur dioxide
Sulphuric acid
Toluene
Triethyl amine
Vinyl chloride
Xylene
HCl
HCN
H 2S
H 2N=NH 2
Hg
HOH2C-NH2
NO
HNO3
NO2
O3
C6H 5OH
SbH 3
SO2
H2SO 4
C6H 5CH 3
(H5C2) 3.N
H 2C=CH.Cl
(CH 3C) 2C6H 4
0.10
50
10
5000
50
1
3
1000
4 per cent
(explosive level)
5
10
20
1
1000
0.1 (mg/m3)
3
25
2
5
0.1
1000
100
5
0.1
5
1 (mg/m3)
200
25
1
100
H2
* Other than those given in italic, all other MACs are specified by OSHA-1982.
APPENDIX F
SUITABLE TECHNIQUES FOR

MEASUREMENT OF SUBMARINE AIR
POLLUTANTS
Pollutant
Range of
measurement
(ppm)
Carbon monoxide
Carbon dioxide 0-5000
Hydrogen
0-4%
Oxygen
0-25%
Hydrocarbon
0-1000
Acrolein
* Technique of measurement used
0-50
+
+
+
+
+
+
+
+
+
+
+
Formaldehyde
0-2
Monoethanol
amine
0-2
Chlorine
Halocarbon
0-25
+
+
+
+
+
+
Ammonia
Stibine
0-1
Sulphuric
acid aerosol
0-1 mg
9*
+
+

Chemical method
NDIR method
Electrochemical method
Photoacoustic method
GCMS technique
Thermal conductivity method
Paramagnetism technique
1.
2.
3.
4.
5.
6.
7.
8.
9.
Hydrazine
+ = applicable technique
+
+
+
+
Nitrogen
dioxide
0-1000
Hydrogen chloride
INDEX
A
ACGIH
50
Acidosis
39, 42
Acrolein
71, 87
Activated carbon
98
Active carbon 97
Aerosol
108
Air cleaning process 85
Ammonia
78
Electochemical analyser 63
Electrochemical oxidation 60
Emergency surfacing
23
EPA
51
Escape chamber
87
Escape operation
22
Exposure
37
B
Ballast tanks
Battery room
9
11
C
Carbon dioxide 31, 39, 62
Carbon monoxide 30, 38, 58,
60
Carbon monoxide conversion
96
Carboxyhaemoglobin 38
Chemical detector tube 67
Chemicassette 75, 114
Chlorate candles 92
Chlorine
36, 40, 73
Combat information centre
(CIC)
11,12
Comfort
12
Comowarn 60
Continuous monitoring 58
D
Detector tube 60, 71, 73, 74,
76, 77, 78, 81
Dose 37
F
Fast surfacing 87
Freon
88
Freon meter
70
Fromaldehyde
72
Gas chromatography-mass
spectrometry (GC-MS) 116
Gas chromatograph(GC)
68
Grab sampling
58
H
Halocarbons 21, 75
Hopcalite 97
Hydrazine 35, 40, 77
Hydrocarbons
35, 67
Hydrogen 32, 64
Hydrogen chloride 76
Hydrogen eliminators 96
Hydroplanes 4, 23
I
Integrated sampling
58
Iodine pentoxide 61
Ion selective electrode
method
79
124
L
Liquefied oxygen
Lithium hydroxide
92
104
M
Mass-Balance Equation
53
Mercury
88, 111
Metabolic process control
85
Methanometer
67
Methyl fluorone
80
Microbes
36
Molecular sieves
100, 101
Monoethanolamine 36, 73
N
Nitrogen dioxide
75
Non-dispersive infrared (NDIR)
58, 67
O
Operations control
85
Organics 33, 40, 71
OSHA
51, 52, 120
Oxides of sulphur & nitrogen
33, 40
Oxygen
65, 91
P
Paramagnetic oxygen analyser
65
Periscope depth 4, 19
Personal monitors
58
Photoacoustic spectrometry 68
Photoacoustic spectroscopic
analysis (PSA) 117
Polynuclear aromatic 69
Polynuclear aromatic hydrocarbons 68, 69
Polynuclear aromatic hydrocarbons (PAH)

33
Potassium superoxide 105
63, 67
Pressure hull 9,12
Pressure swing molecular
adsorption (PSMA) 103
Propeller
4
Propellar shaft11
R
Refractive index 63
Remedies 42
Rhodamine method
Risk assessment
Rudder
4, 11
79
44, 45
S
Sampling techniques 57
Scrubber 105
Scrubber designs 20
Scrubbers 19, 87
Snorkel
4, 18
Snorting 19
Snorting at Snorkel
6
Sodalime 103, 104
Solid amine scrubber 107
Solid polymer electrolysis (SPE)
94
Sonar domes
6
Stibine (SbH ) 32, 40, 79
3
Sulphuric acid aerosol 32, 40,
81
Synergistic effects
41
Temperature swing molecular

adsorption (TSMA)
102
Thermal conductivity 64
Torpedo tubes
11
TWA 51

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ENVIRONMENT IN SUBMARINES

MVR Koteswara Rao

DEFENCE RESEARCH & DEVELOPMENT ORGANISATION

DRDO Monographs/Special Publications Series

Ashok Kumar, A Saravanan

2001, Defence Scientific Information & Documentation Centre

Printed and published by Director, DESIDOC, Metcalfe House, Delhi-110 054.

How Does a Submarine Function?

Men & Metabolic Activity

Typical Calculation of Carbon Dioxide

Metabolic Organic Compounds

Engines & Batteries

Panelling, Flooring & Degreasing

Sulphuric Acid Aerosol

Oxides of Sulphur & Nitrogen

Polynuclear Aromatic Hydrocarbons

Oxides of Sulphur & Nitrogen

Sulphuric Acid Aerosol

Effect of Indoor Air Pollution in Submarine

Role of Risk Assessment in Submarine

Development of OSHA, ACGIH & Submarine

Non-Dispersive Infrared Absorption

Iodine Pentoxide Method

Refractive Index Method

Chemical Detector Tube Method

Thermal Conductivity Analyser

Mass Spectrometric Method

Paramagnetic Oxygen Analyser

Chemical Detector Tube

Gas Chromatographic Techniques

Polynuclear Aromatic Hydrocarbons

Collection of Polynuclear Aromatic

Detection of Polynuclear Aromatic Hydrocarbons

IR and PAS Techniques

Oxidation with Iodine

Oxidation with KMnO4

Detector Tube Method

Ion Selective Electrode Method

Methyl Fluorone Method

Detector Tube Method

Sulphuric Acid Aerosol

High Pressure Gas Storage

Oxygen Supply from Water Electrolysis

Solid Polymer Electrolysis

Carbon Monoxide Conversion

Metal-impregnated Active Carbon

Carbon Dioxide Control

Adsorption on Molecular Sieves

Temperature Swing Molecular Adsorption Process

Pressure Swing Molecular Adsorption Process

Carbon Dioxide Removal using Wet MEA

Solid Amine Scrubber

MVR Koteswara Rao

The submarine is a sea-going vessel designed to navigate

First war submarine

Sank the warship

First use of diesel engine

World War I naval

First American submarine

Snorkel attachment for

First nuclear powered

Crosses the North Pole

Worlds largest submarine

First Polaris carrying